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The Power of Independent Thinking
C.S. Lewis on Mere Liberty and the Evils of Statism
Recorded: Saturday, August 2, 2014
David J. Theroux, founder and president of The Independent Institute and the C.S. Lewis Society of California, discusses the writings of C.S. Lewis and Lewis's views on individual liberty, natural law and statism.
The presentation was the keynote talk at the first annual conference of Christians for Liberty, that was held at St. Edwards University in Austin, TX, August 2, 2014.
Experts: David J. TherouxType: Other EventIssues: Bureaucracy and Government, Civil Liberties/ Human Rights, Collectivism, Culture/ Society, Education, Family, Freedom, Government Power, Political Ideology and Philosophy, Politics, Privacy, Privatization, Property Rights, Regulation and Deregulation, Religion, Science, Taxes, Welfare
Robert Higgs Discusses Effects of WWI on the Tom Woods Show
Recorded: Wednesday, July 30, 2014
Sr. Fellow Robert Higgs appeared on the Tom Woods radio show. Higgs discusses the 100th anniversary of the outbreak of World War I and its devastating effects on people and government.
Experts: Robert HiggsType: RadioIssues: Defense and Foreign Policy, Economic History and Development (International), Economic History and Development (U.S.), Economic Policy, Free Market Economics, History (International), History (U.S), Political Ideology and Philosophy
Robert Higgs on FDA and Consumer Welfare
Recorded: Wednesday, July 23, 2014
This presentation by Independent Institute Senior Fellow Robert Higgs was presented on July 24, 2014, at Mises University, sponsored by the Ludwig von Mises Institute, in Auburn, Alabama.
Experts: Robert HiggsType: Other EventIssues: Economists, Free Market Economics, Government Power, Regulation and Deregulation
Robert Higgs: The Welfare State
Recorded: Tuesday, June 17, 2014
Robert Higgs discusses the rise of the welfare state in the United States.
For information on The Challenge of Liberty Summer Seminar, click here.
Experts: Robert HiggsType: Challenge of Liberty SeminarsIssues: Bureaucracy and Government, Corporate Welfare, Economic History and Development (International), Economic History and Development (U.S.), Economic Policy, Free Market Economics, Government Power, Government Waste/Pork, History (U.S), Labor and Employment, Political Ideology and Philosophy, Regulation and Deregulation, Social Security, Welfare
Robert Higgs - Crisis, Leviathan, and the National Security State
Recorded: Thursday, February 27, 2014
"Crisis, Leviathan, and the National Security State" by Robert Higgs was a speech sponsored by The Future of Freedom Foundation February 15, 2014 at the 2014 International Students for Liberty Conference in Washington D.C.
Experts: Robert HiggsType: TelevisionIssues: Constitutional Law, Defense and Foreign Policy, Economic Policy, Free Speech, Freedom, Government Power, History (U.S), Nationalism, Political Ideology and Philosophy, Politics, Privacy, Terrorism and National Crises
The State Is Too Dangerous to Tolerate
Recorded: Saturday, July 27, 2013
Robert Higgs, Senior Fellow at the Independent Institute and author of Delusions of Power, speaks at the 2013 Mises University, hosted by the Mises Institute in Auburn, Alabama, on 27 July 2013.
Experts: Robert HiggsType: TelevisionIssues: Civil Liberties/ Human Rights, Defense and Foreign Policy, Government Power, Political Ideology and Philosophy
Civil Liberties and Security in an Age of Terrorism
Recorded: Thursday, July 18, 2013
Civil Liberties in an Age of Terrorism: A special evening with our "Challenge of Liberty Summer Seminars" students and featured by C-SPAN's Book TV. Watch this eye-opening, timely discussion on the recent revelations of systematic government spyingincluding NSA accessing of phone records, USPS photocopying the exterior of all mail, and the dangers posed to liberty and security by these and other such unchecked and unconstitutional powers.
Experts: Anthony Gregory, Robert Higgs, Mary L. G. TherouxType: Independent Institute EventIssues: Civil Liberties/ Human Rights, Constitutional Law, Defense and Foreign Policy, Privacy, Terrorism and National Crises
Robert Higgs on Scott Horton Show
Recorded: Tuesday, April 2, 2013
Senior Fellow Robert Higgs talks with Scott Horton about the growth of government during the war on terror, economic recession and domestic emergencies. Check out some of Robert Higgs books mentioned on the program.
Experts: Robert HiggsType: RadioIssues: Bureaucracy and Government, Defense and Foreign Policy, Economic History and Development (U.S.), Economic Policy, Political Ideology and Philosophy


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High school football live stream: Timpview vs. Mountain Crest, 4A championship, Friday 6:30 p.m.
The Deseret News is proud to bring you live streaming coverage of high school events. This event is being produced entirely by volunteers from the community. We appreciate their efforts in helping us to catch kids doing great things.
If this stream is not functioning after 6:30 p.m. MST, please email us
This event also features a live updating box score. The box score is updated after every play.
If youd like to help your school be streamed live, email us at firstname.lastname@example.com.
Our streams are being watched live all over the world. A number of people have told us from where they are watching today's games. Here is a map of the responses we've received from you, the viewer.
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Bypass the box office line at many theaters with guaranteed tickets. If something comes up, you can return or exchange up to two hours before showtime through Fandango.
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Looking for movie tickets? Enter your location to see which movie theaters are playing Underworld U.S.A. near you.
Cliff Robertson plays Tolly Devlin, an embittered ex-convict who has spent a lifetime tracking down the men who murdered his father. Desirous of handling matters on his own, Devlin pretends to be loyal to both the Mob and the Government, playing one against the other in hopes of flushing out the killers. He learns that the three surviving assassins are employed by a supposedly charitable "cover" operation known as National Projects. To get what he wants, Devlin ingratiates himself with mob boss (and outwardly solid citizen) Conners (Robert Emhardt). What Robertson didn't count on was falling in love with "Cuddles" (Dolores Dorn), which leads to his own downfall -- but not before justice is served. Producer/director/writer Fuller based Underworld USA on a series of "exposé" articles in The Saturday Evening Post; the film's release fortuitously occurred shortly after that infamous mob convention in Appalachin, New York. ~ Hal Erickson, Rovi


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Heat's All-Star venture coming along
Originally Published: February 19, 2010By Brian Windhorst | ESPN.com
The Heat spent their last week before the All-Star break on a road trip through the North, and without really expecting it, the time afforded them a chance to truly take stock of where this high-pressure season is taking them.
The news has been both good and bad.
In the short run, the Heat have stared a truth in the face. They are a flawed team in several respects, with issues at point guard and center and a massive problem located in Boston. The Heat haven't beaten the defending ...
Read full story
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- Doolittle: Are the Bulls a legit contender?
- Ford/Pelton: 2015 NBA Future Power Rankings
- Doolittle: Bucks better than their projection
- Pelton: Hornets' face bleak playoff hopes
- Haberstroh: Markeiff Morris could struggle


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New Arrivals
You are paying good money for your Halloween costume, so don't end up with something from the back of the closet! Our New for 2014 costume selection is full of our newest outfits. Many of these men's costumes are inspired by the latest blockbuster movies and trends in popular culture. 2015 as a big year for superhero movies. Browse our brand new costumes for heroes like Captain America, Spiderman, and Thor. Not every new costume is from a popular TV show or film.
The Simpson's Homer Deluxe Costume for Men
Wanna See My Nuts Costume for Men
Native American Costume For Adults
Mr. Incredible Bodysuit Skinovation Costume for Men
The Muppets Kermit Deluxe Costume for Men
Avengers 2 Hulk Top Costume for Men
Avengers 2 Captain America Top Costume for Men
Hooded Huntsman Costume for Men
Unisex Minions Hoodie for Adults
Iron Man "Mark 43" Top Avengers 2 Costume for Men
Dragon Master Cape Costume for Men
Adult Satin Bat Cape Red Costume for Men
Some of our most unique adult costumes are completely out of the ordinary. If you want a Halloween costume no one else will be wearing, shop our selection of new costumes like our cheeseburger outfit, gorilla suit, and renaissance archer costume. Accessorize your look with the right adult costume accessories and props. Toy weapons, gloves, and boots can add a great level of detail to your outfit. If you would like to attend your next costume party with a friend or significant other, consider pairing up for a couples costume. We have new women's costumes for 2015, so your partner can wear our newest selections too. Match your theme so that you might have two superhero, humor, or monster costumes.


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Most popular at the top
Bird by BirdKnopf Doubleday Publishing Group 2007; US$ 15.95
"Superb writing advice... hilarious, helpful and��provocative." -- New York Times Book��Review . "A warm, generous and��hilarious guide through the writer's world and its��treacherous swamps." -- Los Angeles��Times . "A gift to all of��us mortals who write or ever wanted to write...��sidesplittingly funny, patiently wise and alternately��cranky... more...
Introduction to Documentary, Second EditionIndiana University Press 2010; US$ 20.99
This new edition of Bill Nichols?s bestselling text provides an up-to-date introduction to the most important issues in documentary history and criticism. Designed for students in any field that makes use of visual evidence and persuasive strategies, Introduction to Documentary identifies the distinguishing qualities of documentary and teaches the... more...
Existentialist CinemaPalgrave Macmillan 2009; US$ 115.00
An exploration of the relationship between cinema and existentialism, in terms of their mutual ability to describe the human condition, this book combines analyses of topics in the philosophy of film with an exploration of specific existentialist themes expressed in the films of Fellini, Bergman and Woody Allen, among others. more...
Participatory CompositionSouthern Illinois University Press 2013; US$ 40.00
Like. Share. Comment. Subscribe. Embed. Upload. Check in. The commands of the modern online world relentlessly prompt participation and encourage collaboration, connecting people in ways not possible even five years ago. This connectedness no doubt influences college writing courses in both form and content, creating possibilities for investigating... more...
Television and Radio in the United KingdomUniversity of Minnesota Press 1981; US$ 75.00
Television and Radio in the United Kingdom was first published in 1981. Burton Paulu regards British broadcasting as the best in the world, and ascribes controlled competition as the basic reason for its present status. The BBC, the most highly respected of all broadcasting services, benefited from the creation, in 1954, of the commercially-supported... more...
From Cover to CoverHarperCollins 2010; US$ 9.99
The revised edition of From Cover to Cover offers a fresh, up-to-date look at some of the best examples of children's literature today and also includes practical advice on how to write clearly articulated, reasoned opinions so that others can learn about books they have not yet read. A brief, updated introduction explains how children's books... more...
African American TheatreCambridge University Press 1994; US$ 48.00
This book traces the history of African American theatre from its beginnings to the present. more...
The Intent to LiveRandom House Publishing Group 2004; US$ 16.00
?I call this book The Intent to Live because great actors don?t seem to be acting, they seem to be actually living.? ?Larry Moss, from the Introduction When Oscar-winning actors Helen Hunt and Hilary Swank accepted their Academy Awards, each credited Larry Moss?s guidance as key to their career-making performances. There is a two-year waiting list... more...
PrincessCrown/Archetype 2008; US$ 13.95
Welcome, Your Highness. If you?ve picked up this book, you know who you are. You have a taste for life?s finer things: champagne with breakfast, custom lingerie, and kitten heels?even in the snow. At the office, you?re a corporate merger of style and substance, flawlessly handling the most difficult clients or performing life-saving surgery wearing... more...
Voice WorkWiley 2013; US$ 115.99
Voice Work: Art and Science in Changing Voices is a key work that addresses the theoretical and experiential aspects common to the practical vocal work of the three major voice practitioner professions - voice training, singing teaching, and speech and language pathology. The first half of the book describes the nature of voice work along the normal-abnormal... more...


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2 Results
What Makes a Leader? (HBR Bestseller)Leadership & Managing People Magazine Article8.95When asked to define the ideal leader, many would emphasize traits such as intelligence, toughness, determination, and vision--the qualities traditionally...
PSI India--Will Balbir Pasha Help Fight AIDS? (B)Communication Case Study5.00An abstract is not available for this product.
PSI India--Will Balbir Pasha Help Fight AIDS? (A)Communication Case Study8.95In 2002, Population Services International (PSI) was committed to curbing the growing HIV/AIDS epidemic in India. Sanjay Chaganti, program director of...


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Test: Optical performance of Nikonos 15mm, flat and dome ports
Inventor, manufacturer and filmmaker Pawel Achtel shares his tests of the performance of cinema lenses behind flat and dome ports as well as the use of the Nikonos 15mm wide-angle lens. They were tested using a RED Epic camera in 5K mode, shooting Spatial Frequency Response charts underwater with the camera held in a rigid frame to ensure repeatable results.
Typhoon Hagupit slams into the Philippines
As I write, super Typhoon Hagupit is finding landfall on the eastern coast of the Philippines. It is expected that the accompanying 120mph winds and storm surge are likely to wreak destruction to areas that are still recovering from the devastation wrought by Typhoon Haiyan a year ago. The authorities seem much better prepared this time, and it is hoped that the terrible loss of life that occurred last year will be avoided. Nevertheless, it is inevitable that there will be significant disruption and damage to properties. The Wetpixel community fervently hopes that if you are in the path of the storm, you and your loved ones are in a place of safety and that the the damage to your property and businesses is as limited as possible. You are in our thoughts and prayers.
A failure to evolve may cause the Charles Darwin research station to go extinct
In an unusual twist of fate, the famed Charles Darwin Research Station of the Galapagos Islands may close by the end of the year due to failure to adapt with the times. The legacy of the research station may rest in the hands of donors as the lab is asking for nearly one million dollars in donations prior to the end of the year. Scientists claim the closure of the gift shop left them in this dire predicament.
Seals use acoustic tags to hunt more efficiently
Howard Hall commented here on Wetpixel about the proliferation of tags that are festooning some marine animals and the potential negative effects that these may have on the animals that the studiers seek to understand. A paper published recently in the Proceedings of the Royal Society B entitled Grey Seals use anthropogenic signals from acoustic tags to locate fish shows how grey seals (Halichoerus grypus) have learnt to use the signals emitted by fish tags as an aid to hunting more efficiently.
Keldan ships their Video 8X light
Keldan is now shipping their Video 8X light. Featuring a 10,000 lumen output and a new dome and lens unit, the light will burn for 42 minutes at full power. It has a 90° beam angle (in water) and a CRI of 82 at 5,000°K.
A battle to save the most endangered marine mammal: The Vaquita
The battle to save the Vaquita of the Gulf of California involves an interesting cast of characters: a Mexican drug cartel, Chinese wildlife traffickers, and an endangered fish's swim bladder. Scientists believe the critically endangered porpoises, down to a population of 100, could become extinct within three years if drastic action is not taken.
Help the Shedd Aquarium name their famous sea otter pup
The Shedd Aquarium's rescued California sea otter pup 681 needs a name, and Good Morning America is helping the aquarium to raise awareness and choose a name between five options. You can vote for a winning name in the poll here.
Ikelite releases MIL housings for Olympus mirrorless cameras
Ikelite has launched their MIL system for mirrorless cameras. The first two housings are for the Olympus OM-D E-M10 and PEN E-PL7 cameras. The housings feature Ikelite's TTL strobe triggering system and a new interchangeable lens system. This offers support for Olympus and Panasonic zoom, wide-angle and macro lenses.
Recent News
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The RSPCA says volunteers in Broken Hill have been disturbed by a recent animal cruelty case, where a dog had to have its leg amputated.
Topics: animal-welfare, community-and-society, law-crime-and-justice, courts-and-trials, broken-hill-2880
The Young Shire Council has approved plans to build a skate park in the town, despite almost 90 submissions opposing the development.
Topics: local-government, youth, urban-development-and-planning, young-2594, wagga-wagga-2650
The chief executive of the Northern New South Wales Local Health District says a major restructure of the system announced yesterday will mean less management meddling.
Topics: health-administration, health-policy, programs-and-initiatives, states-and-territories, lismore-2480
The Murrumbidgee Local Health District's management will change under the New South Wales Government's latest health reforms but there is still no detail on how it will happen.
Topics: health-administration, programs-and-initiatives, states-and-territories, health, wagga-wagga-2650, griffith-2680
Hurricane Irene has been battering the Bahamas as it barrels towards the US east coast.
Topics: floods, weather, dominican-republic
Green campaigner Drew Hutton will face court today over his arrest in March at an anti-mining rally on Queensland's western Darling Downs.
Topics: courts-and-trials, activism-and-lobbying, federal---state-issues, mining-environmental-issues, mining-rural, mining-industry, oil-and-gas, chinchilla-4413, tara-4421, bundaberg-4670, toowoomba-4350
Posted| Updated
A 25 year-old man accused of stabbing a police officer is due to appear in court in Port Hedland this morning.
Topics: assault, nullagine-6758
A survey of residents in Bundaberg and the Fraser Coast in southern Queensland has revealed almost 98 per cent of people are against same-sex marriage.
Topics: federal-parliament, activism-and-lobbying, gays-and-lesbians, bundaberg-4670, townsville-4810, parliament-house-2600
Posted| Updated
New Zealand coach Graham Henry has named a near full-strength line-up for the Tri Nations title decider against Australia.
Topics: rugby-union, sport, new-zealand, australia, brisbane-4000, qld
The proposed Ryan's Corner and Hawkesdale wind farms in south-west Victoria are in limbo after a Moyne council decision.
Topics: wind-energy, urban-development-and-planning, local-government, hawkesdale-3287, ballarat-3350
Ballarat MP Catherine King has told Federal Parliament a personal meeting with a same-sex couple has made her question her view of gay marriage.
Topics: gays-and-lesbians, marriage, federal-government, ballarat-3350
A bushfire expert says central Victorian forests will not be destroyed by an increase in fuel reduction burning.
Topics: fires, forests, emergency-planning, bushfire, bendigo-3550
Police are investigating an armed robbery in northern Victoria.
Topics: armed-robbery, burglary, courts-and-trials, echuca-3564, bendigo-3550, pyramid-hill-3575
Posted| Updated
North Korean leader Kim Jong-Il has travelled to Russia for the first time in 10 years to hold talks with Russia's president Dmitry Medvedev.
Topics: world-politics, russian-federation
Posted| Updated
Police in Perth continue to hold a 47 year old man in custody over a double murder in the Perth suburb of Maylands.
Topics: murder-and-manslaughter, maylands-6051
Posted| Updated
Woolworths has reported a modest increase in its annual profit, but says the tough conditions for retailers are set to continue.
Topics: company-news, business-economics-and-finance, food-and-beverage, retail, australia
Posted| Updated
Scientists hope an Australian-based trial to eliminate dengue fever will now be rolled out overseas.
Topics: infectious-diseases-other, medical-research, research, cairns-4870, gordonvale-4865, yorkeys-knob-4878, townsville-4810
Queensland Police Superintendent Noel Powers discusses an investigation into a house fire which left 11 people dead in Logan, south of Brisbane.
Topics: residential, emergency-incidents, grief, qld
Posted| Updated
Federal Trade Minister Craig Emerson discusses the controversy embroiling Labor MP Craig Thomson.
Topics: alp, federal-government, federal-parliament, prostitution, australia
Posted| Updated
Native rats in plague proportions are still chewing through cables and wires in outback south-west Queensland and are now annoying campers.
Topics: rural, animals, endangered-and-protected-species, birdsville-4482, mount-isa-4825, longreach-4730
Posted| Updated
New figures show that the state's biggest resource companies donated almost $90 million to northern charities and community groups in the past year.
Topics: community-organisations, mining-industry, broome-6725, karratha-6714
Posted| Updated
Former South Sydney and Parramatta coach Jason Taylor says he is interested in the Bulldogs' vacant coaching position.
Topics: nrl, rugby-league, sport, canterbury-2193, belmore-2192, nsw, australia
Southern Queensland independent MP Dorothy Pratt says she is worried about the future of small towns that are not covered by legislation protecting communities from mining.
Topics: state-parliament, activism-and-lobbying, federal---state-issues, mining-rural, mining-environmental-issues, regional-development, mining-industry, regional, community-development, nanango-4615, maroochydore-4558, bundaberg-4670, toowoomba-4350
The Tasmanian Independent, Andrew Wilkie, is being accused of misrepresenting his Denison electors on the issue of same sex marriage.
Topics: sexuality, government-and-politics, tas, hobart-7000
Victoria Police are appealing for a person who was due to meet a Cranbourne man just before his death to contact them.
Topics: murder-and-manslaughter, crime, cranbourne-3977


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See other Gent properties
Ecohostel Andromeda
Real Reviews
Real reviews from fellow travellers
These are trusted reviews from guests who have actually stayed here. We hope you find them helpful.
Note: we only give a property a rating once it has received a minimum of 3 reviews.
- Page:1/1
- " Staying on a boat is just awesome, great showers, cool sleeping and breakfast rooms, good wifi. i would go here again! "
- 10 Jul 2015 Anonymous Netherlands
- " Didnt really read up about where we were staying- when we saw the boat we were very pleased. It was a lovely boat, good comfy beds and a very nice breaky. "
- 05 Jun 2015 mira Australia
- " Thanks a lot. It was very good! "
- 01 Nov 2014 Natalia Colombia
- " We had a great stay in Gent. Sleeping on a boat is great, the interior is really cool and the breakfast was really delicious. The city centre is in walking distance. We also got great tipps for the rest of our journey. "
- 13 Oct 2014 Marei Germany


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Angel Escobar's awareness of motion is one of the many elements that make his poems undeniably powerful. To me, as I translate his poems, there is no doubt that Escobar (1957-1997) created multivalent, energetic work, and that a quick reading of one or two poems at least hints at his range. Other writers, at the very least other poets, must recognize the surety of his movements.
What if you could identify the applause in every recording in the PennSound archive?
Kia ora ano.
In te ao Māori [the world of the Māori] everything is intensely interrelated, which is why all of these conversations-commentaries keep on interconnecting. So when Alison Wong writes about Pauatahanui, it segues into what I wanted to write next. It was once the home of a poet who is mainstream, but has never been any favourite of this country's academic mainstream.
Translation from Yiddish by Ariel Resnikoff & Stephen Ross
At some point, yesterday or long ago, you read a poem and something happened to you: and you thought, or you didn't quite think: yes. And this affirmative recognized a need, or a touch, or more precisely an answer to a question you hadn't even asked. The question hadn't existed until the work appeared to create it, opening that space, revealing a gap.


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- World
At least 16 dead in French Riviera flash floodsAt least 16 dead in French Riviera flash floodsForecasters said the the worst of the storms have passed.
- News
Can you pass this Cajun quiz?Can you pass this Cajun quiz?We've put together this little GRA quiz for you to pit your wits against yourself and your friends.
- Entertainment
French, Spanish wines offer elegance, finesseFrench, Spanish wines offer elegance, finesseFrançois Lurton is no newcomer to the winemaking business.
- World
French warplanes 'totally destroyed' Islamic State camp in SyriaFrench warplanes 'totally destroyed' Islamic State camp in SyriaSunday's strike was the first time the French attacked the Islamic State in Syria.
- World
Mont Blanc Glacier feels the cold from climate changeMont Blanc Glacier feels the cold from climate changeWe are just months away from the COP21 summit taking place in December, where almost 200 nations will head to Paris to discuss climate change. Global warming is starting to have a visible impact in the Alps mountain chain.
- News
Fife and drum groups play in PalmyraFife and drum groups play in PalmyraLocal and international drummers brought traditional music to Palmyra Canal Days Saturday.
- World
French winemakers hunt for climate change-resistant grapeFrench winemakers hunt for climate change-resistant grapeAmid the bustle of a busy harvest in France's famed Beaujolais wine-making region, a quiet effort is underway to counter one of the industry's biggest potential threats: climate change.
- Travel
The Upper Marais: An up-and-coming Paris neighborhoodThe Upper Marais: An up-and-coming Paris neighborhoodParis is full of charming neighborhoods like the buzzed-about Upper Marais. Let T+L steer you to the area's best pastry shops and boutiques.


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- 800.878.7323
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Other titles in the Manga Guide To... series:
The Manga Guide to Databasesby Mana Takahashi
Synopses & Reviews
Publisher Comments:
Every day researchers face an onslaught of irrelevant, inaccurate, and sometimes insidious information. While new technologies provide powerful tools for accessing knowledge, not all information is created equal. Valuable information may be tucked away on a shelf, buried on the hundredth page of search results, or hidden behind digital barriers. With so many obstacles to effective research, it is vital that higher education students master the art of inquiry.
Information Now is an innovative approach to information literacy that will reinvent the way college students think about research. Instead of the typical textbook format, it uses illustrations, humor, and reflective exercises to teach students how to become savvy researchers. Students will learn how to evaluate information, to incorporate it into their existing knowledge base, to wield it effectively, and to understand the ethical issues surrounding its use. Written by two library professionals, it incorporates concepts and skills drawn from the Association of College and Research Libraries' Information Literacy Competency Standards for Higher Education and their Framework for Information Literacy for Higher Education. Thoroughly researched and highly engaging, Information Now offers the tools that students need to become powerful consumers and creators of information.
Whether used by a high school student tackling a big paper, an undergrad facing the newness of a university library, or a writer wanting to go beyond Google, Information Now is a powerful tool for any researcher's arsenal.
The Manga Guide to Databases capitalizes on the international manga phenomenon. This first in a series of EduManga titles from No Starch Press (co-published with Ohmsha, Ltd. of Japan) uses manga to teach the reader about databases. Rather than learning from a dry textbook, readers follow the animated adventures of Tico the Database Fairy (picture an anime Tinkerbell) as she interacts with a colorful cast of characters. Combining technical information with fun stories and illustration, the book covers a thorough array of foundational database knowledge including relational databases, database design, E-R models, SQL, operations, and more. Other titles in the series will cover topics like statistics, electricity, and physics.
Information literacy is generally defined as the ability to recognize situations in which information is needed and to find, evaluate, and effectively use relevant information from a variety of media. It is an essential skill set in all academic disciplines at all levels of education and also in professional and personal life. The recent dramatic changes in the technologies of creating, storing, and retrieving content have made information at once more accessible but also more difficult to critically evaluate, and universities have increasingly come to recognize that effective instruction in information literacy is essential to incoming students success in their academic careers and beyond. With that goal in mind, Matt Upson, C. Michael Hall, and Kevin Cannon have created a unique guide in graphic-novel format that instructs undergraduate students in the fundamental research skills that constitute information literacy that is both academically sound and wildly imaginative and engaging. Following the Association of College and University Libraries Information Literacy Competency Standards for Higher Education, the guide stresses skills such as determining the extent of information needed for a research project, accessing the needed information effectively and efficiently, evaluating information and sources critically, incorporating selected information into ones knowledge base, using information effectively to accomplish a specific purpose, and understanding the economic, legal, and social issues surrounding the use of information. Each of the eight chapters ends with exercises that allow students to apply their knowledge to relevant scenarios, and the manuscript concludes with a glossary of critical terms.
Want to learn about databases without the tedium? With its unique combination of Japanese-style comics and serious educational content, The Manga Guide to Databases is just the book for you.
Princess Ruruna is stressed out. With the king and queen away, she has to manage the Kingdom of Kod's humongous fruit-selling empire. Overseas departments, scads of inventory, conflicting prices, and so many customers! It's all such a confusing mess. But a mysterious book and a helpful fairy promise to solve her organizational problems-with the practical magic of databases.
In The Manga Guide to Databases, Tico the fairy teaches the Princess how to simplify her data management. We follow along as they design a relational database, understand the entity-relationship model, perform basic database operations, and delve into more advanced topics. Once the Princess is familiar with transactions and basic SQL statements, she can keep her data timely and accurate for the entire kingdom. Finally, Tico explains ways to make the database more efficient and secure, and they discuss methods for concurrency and replication.
Examples and exercises (with answer keys) help you learn, and an appendix of frequently used SQL statements gives the tools you need to create and maintain full-featured databases.
(Of course, it wouldn't be a royal kingdom without some drama, so read on to find out who gets the girl-the arrogant prince or the humble servant.)
This EduManga book is a translation of a bestselling series in Japan, co-published with Ohmsha, Ltd., of Tokyo, Japan.
About the Author
Trend Pro, Inc. is a pioneer of Ad-Manga--advertisement and advertising using Manga--in Japan. The company has produced over 1,700 Ad-Manga for over 700 clients, including many well-known public companies and government agencies. The company has over 100 registered professional Manga artists.
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|Publication number
|Publication type
|Application number
|Publication date
|Apr 6, 1993
|Filing date
|Jun 20, 1991
|Priority date
|May 26, 1989
|Fee status
|Publication number
|Marie Angelopoulos, Wu-Song Huang, Richard D. Kaplan, Marie-Annick Le Corre, Stanley E. Perreault, Jane M. Shaw, Michel R. Tissier, George F. Walker
|Original Assignee
|International Business Machines Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (2), Non-Patent Citations (2), Referenced by (31), Classifications (34), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a division of application Ser. No. 07/357,565, filed May 26, 1989.
This invention relates to electrically conductive polymers, electrically conductive resists, uses thereof and structures fabricated therewith. More particularly, this invention relates to electrically conductive substituted and unsubstituted polyanilines, substituted polyparaphenylenevinylenes, substituted and unsubstituted polythiophenes, polyazines, substituted polyfuranes, substituted polypyrroles, substituted polyselenophene, substituted and unsubstituted poly-p-phenylene sulfides and polyacetylenes formed from soluble precursors and to selectively forming conducting patterns in these materials and the use of these materials as an electrical discharge layer.
Electrically conducting organic polymers have been of scientific and technological interest since the late 1970's. These relatively new materials exhibit the electronic and magnetic properties characteristic of metals while retaining the physical and mechanical properties associated with conventional organic polymers. Technological application of these polymers are beginning to emerge. Herein we describe electrically conducting polyparaphenylenevinylenes, polyanilines, polythiophenes, polyfuranes, polypyrroles, polyselenophene, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers.
Selected regions of films of the materials of the present invention can be made conducting upon the selective exposure to a source of energy. These materials can be used to make a patternable conductive resist material and can be used as an electrostatic discharge layer, or as an electromagnetic interference (EMI) layer on the surface of a substrate. Because of the electrostatic properties of these materials they can be used as an electron beam resist which acts as its own discharge layer. Moreover, since the materials of the present invention can be readily removed from a surface on which they are deposited, they can be used as a removable electrostatic discharge layer disposed on a dielectric surface under electron beam microscopic examination, for example in a scanning electron microscope (SEM). A removable electrostatic discharge layer permits SEM analysis without destroying the sample.
The article entitled "Photoinitiated Doping of Polyacetylene", T. Clarke et al., J.C.P. Chem Comm., 1981, p. 384, describes insoluble polyacetylene selectively doped with proton acids. The polyacetylene is impregnated with one of the group of triarylsulfonium and diaryliodonium which are innert to the polyacetylene but which on irradiation with a uv light undergo a photochemical reaction leading to the doping of the polyacetylene to make it conductive. The impregnated film can be selectively exposed to light through a mask to selectively dope selected regions of the polymer. Polyacetylene is not suitable, as a resist material as are the materials of the present invention, since the polyacetylene is not soluble. For a polymer to be suitable as a resist material it must be capable of having a preselected pattern formed therein, for example on exposure to radiation, with either the exposed or unexposed region being soluble in a solvent while the other of the exposed or unexposed region is insoluble in the solvent.
The article entitled "Photochemically Doped Polypyrrole" of S. Pitchumani et al., J. Chem. Soc., Chem. Commun., 1983, p. 809, describes photochemically doped polypyrrole using as photochemical dopant diphenyliodoniumhexafluoroarsenate. Doping was accomplished by immersion of the polypyrrole substrate in a solution containing the photochemical dopant in methylene dichloride followed by irradiation with a mercury arc. Polypyrrole is not suitable for a photoresist material since the polypyrrole is insoluble.
In both the article of Clarke et al. and the article of Pitchumani et al. an insoluble solid polymer is immersed in a solution containing a dopant material. The dopant material and the solvent are absorbed into the surface of the material. In both cases the solvent in combination with the dopant is exposed to light to render the irradiated part of the polymer electrically conducting. Because of the non-soluble nature of the polymers, the dopants can only be impregnated or absorbed into the surface of the polymer film.
The articles entitled "Polyaniline; Processability From Aqueous Solutions and Effective Water Vapor on Conductivity" to M. Angelopoulous et al., Synthetic Metals, 21 (1987) pp. 21-30, and the article entitled "Polyaniline: Solutions, Films, and Oxidation State" to M. Angelopoulous et al., Mol. Cryst. Liq. Cryst 160-151 (1988), describe a chemically synthesized emeraldine base form of polyaniline which is soluble in various solvents. The emeraldine base is doped by reacting, the emeraldine powder or film with aqueous acid solution for several hours, for example, aqueous acetic acid or aqueous HCl. In contradistinction, according to the present invention where conductive polymeric materials are used as a resist material the dopant reagent and polymer are mixed in a solvent which is thereafter dried to remove the solvents to form a solid solution of the dopant reagent and the polymer. The solid solution is then selectively exposed to energy, for example, electromagnetic radiation, heat or an electron beam, which causes the reagent to decompose to dope those regions of the polymer which are exposed to the energy forming a conductive polymer in exposed regions. In the exposed region the polymer is rendered insoluble and in the unexposed regions the polymer is soluble and can thereby be removed to act as a negative photoresist which is selectively electrically conducting. A resist material of this kind is particularly useful for electron beam lithographic applications since the resist material can be its own discharge layer.
One problem associated with electron beam lithography is charging of the electron beam resist. This is particularly significant in microelectronic applications. In microelectronic applications, a pattern in a dielectric layer or an electrically conducting layer, can be formed by depositing a resist material thereover. A commonly used method of selectively removing the resist material is to selectively expose the resist material to an electron beam. The resist material in the exposed region is either made soluble or insoluble upon exposure to the electron beam radiation. The solubility of the unexposed region is opposite that of the exposed region. Therefore, the exposed or the unexposed region can be removed. The resist material is typically a dielectric. When an electron beam is directed at a dielectric surface, charges from the electron beam accumulate on the surface creating an electric filed which distorts the electron beam on the surface resulting in a loss of precision and displacement errors. To avoid charging the resist, it is common practice in the art to coat the resist, prior to electron beam exposure, with a thin conducting metal layer. Most metals, e.g. Au and Pd, are difficult to remove. In some cases the metal deposition process can degrade the lithographic properties of the resist due to heat and stray radiation during deposition. The polymer discharge layers of the present invention can be deposited by a simple spin coat process, whereas a metal cannot.
According to one aspect of the present invention, a resist material is provided which is on selective exposure to energy, for example electromagnetic radiation, an electron beam or heat, rendered insoluble and at the same time electrically conducting. The exposed regions are insoluble and conducting and the unexposed regions are soluble and nonconducting. When the source of energy generating the pattern is an electron beam, the pattern which is conducting forms an electron discharge path preventing distortion of the writing beam. If the dielectric layer on which the resist is deposited is thin, the discharge path does not have to be grounded. This avoids the requirement of depositing a metal layer to act as a discharge layer.
The polymer materials which are made electrically conductive according to the present invention have additional utility in providing an easily processable and low cost EMI (electromagnetic interference) layer which can provide shielding of electrical components from electrical noise.
The conductive polymer materials of the present invention can also be used as an electrical discharge layer for scanning electron microscopic applications. Typically, when a sample is being analyzed under a scanning electron microscope a thin metal layer is coated onto the sample. A commonly used metal layer is gold or a mixture of gold with other metals. This thin metallic layer acts as an electrical discharge layer to prevent the accumulation of electrical charge on the surface of the sample being examined. When a metallic material is used as an electrical discharge layer it cannot be easily removed, therefore, the sample being examined must be discarded. This is particularly costly in microelectronic applications where it may be desirable to examine a semiconductor chip or semiconductor chip packaging substrate with an electron microscope where the chip or substrate is functional and useful. Depositing a thin metallic layer onto a substrate would render the chip or substrate not usable. By using the electrically conducting polymeric materials according to the present invention, a functional sample can be coated with the polymer, subjected to examination under an electron microscope and thereafter the electrically conductive polymer can be easily removed permitting electron microscopic examination of the functioning part and permitting it to be subsequently used.
It is an object of this invention to provide an electron beam resist material which functions as an electrical discharge layer.
It is another object of this invention to provide a resist material whose solubility and conductivity are dependent upon a dopant species generated by exposure of a dopant precursor to energy.
It is another object of this invention, to provide a method of forming a solid solution of a polymer which is selectively transformed to the conducting state by being selectively exposed to a source of energy.
It is another object of this invention to provide a conductive polymeric electromagnetic interference layer.
It is another object of this invention, to provide an electrical discharge layer for substrates exposed to electron beam radiation, wherein the discharge layer is removable.
A broad aspect of this invention is a polymeric material which has selected regions which are electrically conductive and insoluble and wherein non-electrically conductive regions are soluble.
In a more particular aspect of the present invention, the polymeric material has a partially conjugated π system which is extended by the addition of dopants to the polymeric material to provide at least enough π conjugation so that the π conjugated parts of a molecule of the polymer are substantially in contact with the π conjugated parts of an adjacent molecule.
In another more particular aspect of the present invention, the polymer is selected from substituted polyparaphenylenvinyles, substituted or unsubstituted polyanilines, substituted polythiophenes, polyazines, substituted or unsubstituted poly-p-phenylene sulfides, substituted polypyrroles, substituted polyselenophene, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers.
In another more particular aspect of the present invention, a reagent containing a doping species is contained within the polymer matrix. The doping species is capable of dissociating upon the application of energy, such as electromagnetic radiation, an electron beam and heat. The dissociated species dopes the polymer making it electrically conductive.
In another more particular aspect of the present invention, the dopant species is selected from the group of onium salts, iodonium salts, borate salts, tosylate salts, triflate salts and sulfonyloxyimides.
Another more particular aspect of the present invention, is a method of writing and developing a negative image in a polymer wherein the undeveloped portions of the polymer are electrically conducting.
In another more particular aspect of a method according to the present invention, a solution is formed from a polymer having an extended π conjugated system with a doping species and a solvent. The solution is deposited onto the surface of a substrate, dried to remove the solvent leaving a solid solution of the polymer and the doping species on the surface. The solid solution is selectively exposed to energy, for example, electromagnetic radiation, electron beam radiation or heat, to render the selectively exposed regions electrically conductive. The unexposed regions are thereafter removed in a solvent leaving a pattern of an electrically conductive polymer.
In another more particular aspect of the present invention, a substrate is coated with the electrically conductive polymers according to the present invention, wherein the electrically conductive polymer coating acts as an electrical discharge layer.
In another more particular aspect of the present invention, the polymers with the dopant therein according to the present invention are disposed on the surface of a sample for electron beam microscope examination to function as an electrical discharge layer eliminating distortion from accumulated charge on the electron beam irradiated surface.
These and other objects, features and advantages will be apparent from the following more particular description of the preferred embodiments and the figures appended thereto.
FIG. 1 is a UV/visible spectra of the emeraldine base form of polyaniline.
FIG. 2 is the UV/visible spectrum of the emeraldine base form of polyaniline containing an onium salt.
FIG. 3 is the UV/visible spectrum of composition of FIG. 2 after exposure to light at about 240 nm.
FIG. 4 shows UV light induced conducting lines in an emeraldine base/onium salt polymer of the present invention.
FIG. 5 shows the pattern shown in FIG. 4 developed.
FIG. 6 shows a low resolution SEM of a dielectric mask.
FIG. 7 shows a low resolution SEM of the mask of FIG. 6 after the mask has been coated with a conductive polyaniline material.
FIG. 8 is a high resolution SEM dielectric mask.
FIG. 9 is a high resolution SEM of the mask of FIG. 8 coated with an electrically conducting polyaniline material.
FIG. 10 is a photograph of a polyaniline polymer containing an onium salt after exposure to an electron beam to form conducting live therein shown as the dark pattern.
One embodiment of the present invention is a polymeric material which can be used as a negative resist material. The polymer is disposed onto a substrate and selectively exposed to a source of energy. The energy renders the exposed regions insoluble as compared to the unexposed regions and the exposed regions are rendered electrically conductive. These materials are useful as negative resists for microelectronic applications, such as patterning a dielectric or metal layer on the surface of a semiconductor chip or semiconductor chip package substrate. The use of these materials as resist material has particular utility in electron beam lithography.
Resist materials are generally polymers which are dielectrics. If an electron beam is used to write a pattern in a dielectric resist material, electrons can accumulate on the surface of the dielectric resist. These electrons create an electric field which results in distortion of the electron beam which is writing the pattern. State of the art electron beam lithography uses electron beams having a cross-sectional size in the order of a micron and less. It does not take much locally accumulated charge to create a distortion in such a small cross-sectional beam. To avoid this problem it is common practice in the art to deposit over a resist material a thin layer of metal. We have discovered a way of avoiding depositing a thin layer of metal onto a resist material to avoid the charging problem. The polymers of the present invention can be used as a direct substitute for the metal layer. The polymer is deposited onto the surface of the electron beam resist and exposed to a source of energy to render it conducting. The conducting polymers act as a discharge layer.
The polymers used to fabricate the resist materials of the present invention contain a partially conjugated π system. A solution is formed of the polymer. To the solution is added a doping species (dopant precursor) which on exposure to energy generates a dopant which dopes the polymer to the conducting state. The addition of the dopant results in an expansion of the extent of the conjugated π system in the individual polymer molecule. It is not necessary to extend the conjugated π system over the full extent of the molecule. It is only necessary to sufficiently extend the π conjugated system of an individual molecule so that after the solvent is removed the π conjugate part of an individual molecule is adjacent to a part of the π conjugated part of an adjacent molecule. In the π conjugated system an electron is essentially delocalized over the entire π conjugated bonds. These electrons are more loosely bond and are available for electrical conduction. When an electric field is applied, an electron can flow along an individual molecule and hop from one molecule to an adjacent molecule in a region where the π conjugated parts of the adjacent molecules overlap.
To form a negative resist according to the present invention a π conjugated system must be soluble when not exposed to the dopant and insoluble when exposed to the dopant. One possible explanation for the change in solubility upon exposure to the dopant is the following. Dopants can be a cationic species. The dopant transfers positive charges to the π conjugated parts of the polymer through protonation, pseudo protonation or oxidation. The polymer now has positive charges on the backbone and then combine with anions to form ion pairs. It is more difficult for a solvent to have enough solvation energy for these ion pairs than for the pristine polymer.
One type of nonconducting polymer useful to practice the present invention is a substituted or unsubstituted polyaniline having the following general formula: ##STR1## wherein each R can be H or any organic or inorganic radical; each R can be the same or different; wherein each R1 can be H or any organic or inorganic radical, each R1 can be the same or different; x≧1; preferably x≧2 and y has a value from 0 to 1. Examples of organic radicals are alkyl or aryl radicals. Examples of inorganic radicals are Si and Ge. This list is exemplary only and not limiting. The most preferred embodiment is emeraldine base form of the polyaniline wherein y has a value of 0.5.
If the polyaniline base is exposed to a cationic species QA, for example a protic acid wherein Q is hydrogen, the nitrogen atoms of the imine part of the polymer become substituted with the Q cation to form an emeraldine salt as shown in the following equation: ##STR2##
When a protic acid HA is used to dope the polyaniline, the nitrogen atoms of the imine part of the polyaniline are protonated. The emeraldine base form is greatly stabilized by resonance effects as is shown in the following sequence of equations: ##STR3##
The charges distribute through the nitrogen atoms and aromatic rings making the imine and amine nitrogens indistinquishable. For the sake of simplicity the above sequence of equations was shown with a protonic acid HA. However, a cationic species represented by Q A can also be used whereas Q is a cation selected from organic and inorganic cations, for example, an alkyl group or a metal, being most preferably H.
The emeraldine base form of polyaniline is soluble in various organic solvents and in various aqueous acid solutions. Examples of organic solvents are dimethylsulfoxide (DMSO), dimthylformamide (DMF) and N-methylpyrrolidinone (NMP). This list is exemplary only and not limiting. Examples of aqueous acid solutions is 80% acetic acid and 60-88% formic acid. This list is exemplary only and not limiting. Substituted polyanilines are soluble in more solvents such as chloroform and methylenechloride.
A powder of the emeraldine base is mixed in a solvent with a radiation sensitive onium salt. Upon exposure to radiation the onium salt produces free acid which protonates the emeraldine base to yield an emeraldine salt. Anything that generates a cationic species upon electromagnetic or electron beam radiation can dope the polyaniline polymer.
Examples of suitable onium salts include aromatic onium salts of Group IV elements discussed in U.S. Pat. No. 4,175,972, disclosure of which is incorporated herein by reference, and aromatic onium salts of Group Va elements discussed in U.S. Pat. No. 4,069,055, disclosure of which is incorporate herein by reference.
Aromatic Group IVa onium salts include those represented by the formula:
[(R)a (R1)b (R2)c X]d + [MQe ]-.sup.(e-f)
where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radial selected from alkyl, cycloalkyl and substituted alkyl, R2 is a polyvalent organic radical forming a heterocyclic or fused ring structure selected from aliphatic radicals and aromatic radicals, X is a Group IVa element selected from sulfur, selenium, and tellurium, M is a metal or metalloid, Q is a halogen radical, a is a whole number equal to 0 to 3 inclusive, b is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 or 1, where the sum of a+b+c is a value equal to 3 or the valence of X,
f=valence of M and is an integer equal to from 2 to 7 inclusive, e is >f and is an integer having a value up to 8.
Radicals included by R are, for example, C.sub.(6-13) aromatic hydrocarbon radicals such as phenyl, tolyl, naphthyl, anthryl, and such radicals substituted with up to 1 to 4 monovalent radicals such as C.sub.(108) alkyl such as methyl and ethyl, substituted alkyl such as --C2 H4 OCH3, --CH2 COOC2 H5, --CH2 COCH3, etc. R2 radicals include such structures as: ##STR4##
Complex anions included by MQe - (e-f) of Formula I are, for example, BF4 -, PF6 -, SbF6 -, FeCl6 -, SbCl6 -, BiCl5 -, AlF6 -3, GaCl4 -, InF4 -, TiF6 -, ZrF6 -, etc., where M is a transition metal such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs, rare earth elements such as the lanthanides, for example, Ce, Pr, Nd, etc., actinides, such as Th, Pa, U, Np, etc. and metalloids such as B,P and As.
Group IVa onium salts included by Formula I are, for example: ##STR5##
Aromatic group Va onium salts include those represented by the formula:
[(R)a (R1)b (R2)c X1 ]d + [MQa ]-(e-f)
where R is a monovalent aromatic organic radical selected from carbocyclic radicals and heterocyclic radicals, R1 is a monovalent organic aliphatic radical selected from alkyl, alkoxy, cycloalkyl and substituted derivatives thereof, R2 is a polyvalnet organic radical forming an aromatic heterocyclic or fued ring structur ewith X1, X1 is a Group Va element selected from N, P, As, Sb, and Bi, M is a metal or metalloid, Q is a halogen radical, a is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 to 2 inclusive, and the sum of a+b+c is a value equal to 4 or the valence of X1,
f=valence of M is an integer equal to from 2 to 7 inclusive, e is >f and is an integer having a value up to 8.
Radicals included by R are, for example, C.sub.(6-13) aromatic hydrocarbon radicals such as phenyl, tolyl, napthyl, anthryl and such radicals substituted with up to 1 to 4 monovalent radicals such as C.sub.(1-8) alkoxy, C.sub.(1-8) alkyl, nitro, chloro, and hydroxy; arylacyl radicals such as phenylacyl; arylalkyl radicals such as pyridyl and furfuryl; R1 radicals include sub (1-8) alkyl, C.sub.(3-8) cycloalkyl, substituted alkyl such as haloalkyl, for example, choroethyl; alkoxy such as OCH2 C6 H5 and OCH3 ; alkoxyalkyl such as --C2 COCH3 ; alkylacyl such as --CH2 COOC2 H5 ; ketoalkyl such as --CH2 COCH3.
Radicals included by R2 are, for example: ##STR6## where Q is selected from O, CH2, N, R, and S; Z is selected from --O--, --S-- and ##STR7## and R' is a monovalent radical selected from hydrogen and hydrocarbon. Complex anions included by MQe - (e-f) are, for example, BF4 -, PF6 -, AsF6 -, FeCl4 -, SnCl6 -, SbCl6 -, BiCl5 -, where M is more particularly a transition metal such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn and Co; rare earth elements such as the lanthanides, for example, Ce, Pr and Nd; actinides such as Th, Pa, U and Np; and metalloids such as B, P and As.
Anions which are slightly hydrolyzed, e.g. SbF5 OH--are considered to be the full equivalent if the inhydrolyzed from of the anion for the purposes of the present invention.
To 30 ml of NMP (N-methyl pyrrolidinone) was added 1.5 g of an emeraldine base powder and 9 g of triphenylsulfonium hexafluoroantimonate. The solution was spin-coated onto quartz and silicon wafers to yield a film of approximately 2400 angstroms. FIG. 1 shows a uv/visible spectrum of this film. The peaks at 320 nm and 610 nm are characteristic of emeraldine base as seen by comparison with the uv/visible spectrum of emeraldine base alone shown in FIG. 2.
The film is dried to remove the solvent. Upon exposure to radiation using a 240 nm filter which was selected for the sensitivity of the onium salt used, the uv/visible spectrum of the emeraldine base film contained the onium salt changes. (It is not necessary to filter the radiation flooding exposure at all wavelengths can be used.) The peaks characteristic of the insulating emeraldine base decrease and there is an appearance of an absorption peak around 850 nm which is characteristic of the conducting emeraldine salt. The conductivity of the exposed film was measured using a four point probe to be approximately 1.6 ohm-1 cm-1. It will be recognized by those of skill in the art that the conductivity can be controlled by controlling the amount of onium salt added to the polyaniline and by the amount of time to which the polymer and onium salt combination is exposed to the radiation. The polyaniline becomes insoluble upon exposure. In prior art methods, an emeraldine base is mixed in solution with an acid which protonates the emeraldine base in solution. In contradistinction, according to the present invention, an onium salt is mixed with the emeraldine base solution, the onium salt does not protonate the polymer to be conductive at this point. The solution is disposed onto the surface of a substrate and the solvent is removed by heating to result in a solid solution of the polymer with the onium salt embedded therein. The polymer at this point is still not conductive. Only after exposure to electromagnetic radiation, most preferably UV light, or an electron beam does the polymer become conducting.
FIG. 4 shows a photograph showing an example of the polyaniline onium salt polymer mixture exposed to radiation through a mask to form conducting lines which appear dark in the figure. There is a color change upon exposure. The nonconducting form is blue and the conducting or exposed form is green. The width of these conducting lines are about 2 microns.
FIG. 5 is photograph of the pattern of FIG. 4 with the parts of the polymer which have not been exposed to radiation removed by exposure to an organic solvent such as, those listed above. Therefore, a negative resist material resulting in conducting lines has been formed.
FIG. 10 shows a photograph of a polyaniline onium salt combination which has been selectivly exposed to an electron beam to form conducting line having conductivity of 10-2 OHM-1 CM-1, width 0.5 um and 1.0 um spacing.
The present invention is applicable to a substituted polythiophene. Polythiophenes have general formula: ##STR8## wherein each R2 is H or any organic or inorganic radical; wherein t≧1 and wherein at least one R2 is not H.
It is known in the art that conducting forms of polythiophene are soluble in organic solvents such as nitrobenzene, THF--CH2 Cl2 --CH3 CHCl3 (4;1;1) and in tetrahydronaphthalene. Since these solvents have either a high boiling point or are poisonous, they are unacceptable for a manufacturing environment. It is also know in the art that the polythiophene can be converted to a conducting form upon treatment with a solution of I2, NOBF4, AsF5 and SbF5. These chemicals can corrode electronic components and therefore are unsuitable for electronic applications. Also, the use of these chemicals requires an additional step in the process, first, the polythiophene must be deposited on a substrate and then treated with these chemicals. In contradiction, according to the present invention an onium salt, iodonium salt, a triflate salt, a borate salt, a tosylate salt, a sulfonyloxyimide, or any reagent (referred to herein as a dopant precursor) or oxidizing (a dopant) which dissociates upon exposure to a source of energy to a cationic species is mixed in solution with the polythiophene, deposited on the substrate, dried to remove the solvents and then exposed to either electromagnetic radiation for example, UV radiation an electron beam, or heat, to convert the polymer to the conductive state.
It is believed that the acid generated by the photodecomposition or electron beam decomposition of the onium salt or the sulfonyloxyimide combines with oxygen to oxidize the polythiophene polymer. Polythiophene has a partial conjugated π system. It is believed that the oxidation caused by the decomposed onium salt or the sulfonyloxy imide extends the conjugated π system to induce conductivity in the polythiophene.
Sulfonyloxyimides useful to practice the present invention have the following general formula: ##STR9## wherein R is selected from the group consisting of --CF3, --CF2 CF3 --CF2 CF2 H, --(CF2)--Zn where n=1 to 4, where Z is H, alkyl or aryl, ##STR10## where m is from 1 to 5, and where X and Y (1) form a cyclic or polycyclic ring which may contain one or more hetero atoms, (2) form a fused aromatic ring, (3) may be independently H, alkyl or aryl, (4) may be attached to another sulfonyoxyimide containing residue, or (5) may be attached to a polymeric chain or backbone.
About 345.6 mg of poly(3-butylthiophene) and 230 mg of triphenyl sulfonium hexafluorantimonate in 4 mil xylene and 2 ml NMP were mixed on a roller at 56� C. for one hour. The solution was spin-coated on a silicon wafer containing 5000 Å silicon oxide with spin speed 1200 RPM for 10 seconds. The wafer containing this polymer coating was then baked in a convection oven for 30 minutes at 100� C. After baking it was then subjected to deep UV exposure for 30 minutes. the film turned to black color after exposure. The wafer was then further baked in an oven for 2 hours at 100� C. A conductivity of approximately 0.02 S/cm was measured with 4-probe on the film (1.5 um).
About 156 mg of 3-methylthiophene-3-butylthiophene-copolymer (PMBT) is 3 mil xylene was mixed on a roller at 56� C. The solution was filtered through a funnel having frit size 0.9-1.5 um. Add 117 mg of trifluoromethylsulfonyloxybicyclo (2,2,1)-hept-5-ene-2,3-dicarboximide (MDT) to the solution and mix on roller for 45 minutes. The solution was spin-coated on SiO2/Si wafer with spin rate 2000 PRM for 30 seconds. The wafer was then subjected to UV exposure for 10 minutes and the hot plate for 1 minute at 89� C. A conductivity of 0.04 S/cm was measured on the polymer (approximately 0.4 um) using 4-Probe.
About 600 mg of PMBT was dissolved in a copious amount of xylene (200 ml) then filtered through pressure filter funnel (F frit). The solvent was evaporated and around 5 ml of PMBT in xylene solution was obtained. An amount of 76 mg MDT was added to the solution. The solution was filtered through a 1 um filter tip using a Gastight syringe. The polymer-MDT was spin-coated on to SiO2/Si wafer and then subjected to UV exposure for 15 minutes. After the wafer was baked on a hot plate for 40 seconds at 90� C., a conductivity of 0.1 S/cm was measured on the polymer using 4-probe.
Examples 2, 3 and 4 can be repeated using an electron beam of about 200 μC/cm2 to about 1 mC/cm2 at about 25 KEV.
Polyparaphenylenevinylenes useful to practice the present invention have general formula wherein each R3 is H or any organic or inorganic radical, and wherein s ≧1. Each R3 can be the same or different: ##STR11##
Polyazines useful to practice the present invention have general formula wherein R10 is H or an organic or inorganic radical. ##STR12##
Polyfurans useful to practice the present invention have general formula, wherein Z≧1 and each R4 is H or any organic radical, and each R4 can be the same or different; ##STR13##
Polypyrroles which are useful to practice the present invention have general formula, wherein w≧1, each R5 is H or any organic or inorganic radicals; wherein each one R5 can be the same or different: ##STR14##
Polyselenophene useful to practice the present invention have general formula, wherein v≧1, and each R6 is H or any organic or inorganic radical and wherein each R5 can be the same or different: ##STR15##
Examples of combinations of polythiophenes, polyfurans, polypyrroles and polyselenophene useful to practice the present invention are represented by the following equations wherein R4, R5 and R6 are as defined above wherein at least two of a, b, c and d are greater than or equal to 1; m≧1; Q1, Q2 Q3 can be a vinylene group or a direct bond between adjacent constituents: ##STR16##
Poly-p-phenylene sulfides useful to practice the present invention are represented by the following general formula wherein each R7 is H or any organic or inorganic radical and f≧1, each R7 can be the same or different: ##STR17##
The article entitled "New Routes to Processed Polyacetylenes", T. Swager et al. Polymer Preprints, Vol. 30, No. 1, p. 161, April 1989, describes methods of preparing polyacetalyene from a soluble precursor, the teaching of which is incorporated herein by reference. Polyacetylene is insoluble, therefore, as noted above a conductive resist cannot be made from polyacetylene directly. The soluble polyacetylene precursors of Swager et al. can be used in the structures and methods of the present invention to form a solid solution of polyacetylene and a reagent in which conductivity is induced after exposure to energy. Polyacetylene can be prepared from a number of precursors by the use of ring opening metathesis polymerization (ROMP). Cyclooctatetraene, a high boiling liquid, can be bulk polymerized to polyacetylene. In effect, this provides polyacetylene that can be processed as a viscous liquid. Substituted cyclooctatetraenes can be polymerized or co-polymerized to a soluble polymer that can be easily fabricated. Treatment of the polybenzvalene with Lewis acids results in the rearrangement to polyacetylene.
The polymers of the present invention can be easily spin coated onto a sample and exposed to energy to induce conductivity. The conductive polymers of the present invention can be used as top surface electrical discharge layers or as buried electrical discharge layers for electron beam applications. The conductive polymers according to the present invention are readily etchable in a oxygen plasma. When the polymers of the present invention are used as a buried discharge layer, a first resist layer is deposited onto a substrate, a polymer layer, according to the present invention, is deposited thereover and a second resist layer is deposited onto the polymer layer. The polymer layer can be made conducting by exposure to electromagnetic radiation, an electron beam or heat.
When the conducting polymers according to the present invention are used as a buried discharge layer underneath a dielectric resist layer, the top resist layer still charges up. When exposed to an electron beam the degree of charging depends upon the thickness of this top layer. If the resist material is not too thick charge which accumulates in this top surface layer will leak to the conductive interlayer and flow to ground if the conductive interlayer is grounded. It has been found that the conductive interlayer does not have to be grounded to avoid a distortion of an incident electron beam. It is only necessary that the charge leak away quick enough so as not to build up any significant potential at the electron beam target point.
It has been estimated that a surface conductivity of approximately 10-6 OHM-1 is sufficient to avoid distortion of an incident electron beam of approximately 25 Kev with a dose of 15 μC/cm2. It has been found that this surface resistance will maintain the voltage difference between the target point on the top surface resist and a grounded buried conductive layer at a few volts, preferably less than 1.6 v, when an electron beam voltage of approximately 20 KEV is used. For 1 micron thick film to achieve a surface conductivity of this value a volume conductivity of about 10-2 OHM-1 cm-1 is needed. For a 1,000 angstrom thick film a volume conductivity of about 10-1 OHM-1 cm-1 is needed. We have found no distortion of an electron beam using 0.4 microns of a conductive discharge layer of a polythiophene having a surface conductivity of approximately 4*10-6 OHM-1 under 1 micron of resist even without the discharge layer being grounded. If the resist is grounded we expect a much lower conductivity is required.
The polythiophenes of the present invention have been found to be soluble in tolueneanc xylene and a little less soluble in polar solvents for example THF (tetrahydrofuran), NMP and anisole. Very good mixing has been achieved between the polythiophenes and MDT in xylenes. Enhanced mixing in other solvents may be achievable by incorporating C--O--C linkages or other polar groups as side chains on the thiophene ring of the polymer.
Conductivity of the order of 10 OHM-1 cm-1 can be thermally induced in polymers according to the present invention. The polymeric conductivity is induced thermally by the use of reagents which on heating generate dopants, for example cations. The generated dopants dope the polymer to the metallic regime.
When amine triflates salts are heated they unblock to liberate a free acid, triflic acid, and the volitile amine constituent the temperature at which unblocking occurs depends on the volatility of the amine constituent. The general equation of an amine triflate salt is R3 NIICF3 SO3. Upon the application of heat the salt unblocks to a free acid represented by chemical formula CF3 SO3 H and the volatile amine represented by chemical formula R3 N. The triflic acid is then capable of protonating the polyaniline as described above. Triflic acid is expected to protonate a polyparaphenylenvinylenes, polyazines, polyfuranes, polypyrroles, polyfurances, polypyrroles, polyselenophene, poly-p-phenylene sulfides and polyacetylenes.
An NMP solution of the non-conducting polyaniline containing either diethyl ammonium trifluoromethane sulphonate or diisopropyl ammonium trifluoromethane sulfonate was spin-coated onto quartz wafers to yield thin films of approximately 2,000 angstroms. The films were placed on a hot plate at a temperature range from about 80� to 90� C. for 3 minutes by which time the films displayed a conductivity on the order or about 1 S/cm.
Other examples of triflate salts useful to practice the present invention which are thermally decomposable to a cationic species which can be used to generate dopants useful to practice the present invention includes the triflates, tosylates and borates of the following list:
CF3 SO3 H.(i--C3 H7)2 NH
CF3 SO3 H.(i--C3 H7)2 N(C2 H5)
CF3 SO3 H.(i--C3 H7)2 N(C2 H4 OH)
This list is exemplary only and not limiting.
U.S. patent application Ser. No. 07/322,848 filed on Mar. 14, 1989 to Brunscold et al. entitled "Chemically Amplified Photoresist" the teaching of which is incorporated herein by reference, describes other triflate compounds.
Since acid combines with oxygen to oxidize polymeythythiophene, thermal decomposition of triflate salts should dope polythiophene.
It will be recognized by those of skill in the art that the temperature applied and the time of duration of the applied temperature can be adjusted to achieve different values of conductivity. Any thermally decomposing species which generates a cation or oxide species can be used to thermally induce conductivity in the polymers of the present invention.
The electrically conducting polymers of the present invention have particular usefulness in electron microscopy. Electron microcoscopy is currently used in microelectronics to make observations and dimensional measurements on dielectric masks, for example, quarts/chrome masks used in optical lithography. Charging is caused by the incident electron beam. The current solution to avoid the charging problem is to deposit a thin layer of metal onto the mask. This is, however, a destructive method since complete removal of the metal layer is quite difficult if not impossible. Therefore, scanning electron microscopic observations and measurements are limited to scrapped pieces. Since the conducting polymers of the present invention are readily removable, for example by an oxygen plasma or by undoping in a base, for example, in 0.1M NH4 OH and dissolving off in a solvent, for example, NMP, they can be used as a discharge layer in SEM applications. Since the conductive polymers of the present invention are removable, they can be used as a discharge layer on the surface of masks, electronic devices such as semiconductor chips and semiconductor chip packaging substrates which are not scrap pieces.
Any of the conducting polymers according to the present invention can be used as a discharge layer to avoid distortion in electron beam microscopic observations. For example, a quartz/chromium mask was observed with a SEM at 10 KV at various resolutions. The same mask was coated with an NMP solution of polyaniline which was doped with 1N HCl to result in a conductivity of about 1 S/cm. The coated mask was heated to a temperature of about 80� C. to drive off the solvent. The resulting film thickness was about 1,000 angstroms. The polyaniline coated mask was observed with a SEM. FIG. 6 shows a 256 SEM of a bare quartz/chrome mask. FIG. 7 shows a low resolution SEM of the same mask with a polyaniline coating. FIG. 8 shows a high resolution SEM of a bare mask. FIG. 9 shows a 16.4 KV. SEM of the mask with a polyaniline coating. As can be readily seen from the FIGS. 6-9, the masks which are coated with the conductive polyaniline have a substantially higher resolution than the uncoated mask.
Quite surprisingly it has been found that the minimum surface conductivity of the conductive polymer to avoid resolution distortion due to charging of the observed substrate is about 10-6 OHM-1. Charging was not observed at 10 kv for a conducting polyaniline. Without the conductive coating charging is observed above 2 kv. It is quite surprising that materials having conductivities less than that of metals can act as a discharge layer when they are grounded or not grounded.
For image enhancement in a scanning electron microscope or the like conducting polymers can be made either by techniques known in the art or by techniques described herein. As described above a solution of a proton donor such as HCl and an emeraldine base form of a polyaniline can be mixed in solution which creates a conductive polymer. The solution can be disposed on the sample to be observed under an electron beam. The solvent can be driven off by the application of heat to form an electrically conductive polymer layer. Alternatively, the polymers fabricated according to the present invention can be used. The coated sample can either be exposed to heat or radiation to induce conductivity in the polymer or in the case of the electron beam sensitive cationic species, the electron beam used to make the SEM observation can induce the electrical conductivity in the polymer coating.
After SEM observation the polymer coating can be removed for example using a plasma etch, such as an oxygen plasma or in the case of a polyaniline doped with HCl the conductive polymer can be removed by a wash for example a base, such as KOH, followed by an organic solvent, such as NMP.
The electrically conductive polymer materials of the present invention and other electrically conductive polymers have additional uses such as an electromagnetic interference (EMI) coating on a dielectric surface. For example, electrical components are frequently contained within dielectric housings such as cabinets, molded plastics and the like. To reduce the susceptibility of the electronic components contained within the housing, the dielectric housing can be coated with the polymeric materials of the present invention. This EMI technique is easily implemented in a high volume manufacturing line and has very low cost. Continual EMI coatings contain expensive precious metals such as silver embedded in a polymer matrix.
In summary electrically conductive resist structures and materials have been described which act as their own electrostatic discharge layers. The electrical conductivity can be induced in the polymers of the present invention by exposure to sources of energy such as electromagnetic radiation, an electron beam and heat. The polymers according to the present invention contain π conjugated systems which are extended by exposing to such as dopants a cationic species. The preferred polymers are selected from the group of substituted and unsubstituted polyanilines, polyparaphenylenvinyles, polythiophenes, poly-p-phenylene sulfides, polyfuranes, polypyrroles, polyselenophene, polyacetylenes formed from soluble precursors, combinations thereof and combinations thereof with other materials blends thereof with other polymers and polymers thereof formed from soluble precursors. The polymers can be selectively doped. The polymers are useful as buried and surface electrical discharge layers for electron beam lithography applications and for discharge layers for electronmicroscopy applications for example, scanning electron microscopy.
It is to be understood that the above described embodiments are simply illustrative of the principles of the invention various other modifications and changes may be derived by those of skill in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
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|U.S. Classification
|International Classification
|Cooperative Classification
|European Classification
|Sep 3, 1996
|Fee payment
Year of fee payment: 4
|Sep 18, 2000
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|Oct 20, 2004
|Maintenance fee reminder mailed
|Apr 6, 2005
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|Expired due to failure to pay maintenance fee
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|Sep 3, 2015
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Michigan Stadium during the first period of the Big Chill hockey game between Michigan and Michigan State on Dec. 11, 2010, in Ann Arbor. / KIRTHMON F. DOZIER / DFP
It took a month, but the official attendance figure for the Big Chill at the Big House hockey game between Michigan and Michigan State at Michigan Stadium has grown to 104,073, Guinness World Records said today.
The announced attendance at the Dec. 11 game in Ann Arbor was 113,411, but Guinness originally only verified an attendance of 85,451. That was still good enough to set the world record for hockey attendance, which had been 77,000-plus.
But with the new, final number from Guinness, it's going to be tougher to beat.
In an e-mail to the Free Press today, a Guinness spokesperson said there was an issue with the scanners on the day of the game and "further evidence had to be provided."
The spokesperson said U-M collected complete ticket-scan information, plus camera footage, which was shown to Central Collegiate Hockey Association commissioner Tom Anastos for confirmation.
Case closed!
Incidentally, U-M and MSU meet for the first time since the Big Chill tonight in East Lansing.


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Jake Byrne
Position: TE
Height: 6-4 Weight: 260 lbs.
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DirecTV Sat-Go Gets a $500 Price Drop
For those of you who wanted the Sat-GO, DirecTV's briefcase shaped TV that can pull in satellite broadcasts, but weren't willing to pay the exorbitant $1499 price tag, good news! DirecTV dropped the price of their Sat-Go portable satellite system by $500, to the still relatively expensive price of $999. But hey, $500… »


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The mission of Dream Big! is to help girls from low-income situations achieve their dreams by providing them with the basic items and program fees needed to enable them to participate in sports and physical activities that contribute to their health, education, and overall well-being.
Dream Big! partners with organizations, schools and community health centers in economically disadvantaged communities to identify and fulfill the equipment, uniform, athletic footwear, program fees and training needs of girls from low-income situations, in elementary, junior high and high school in order to help them engage in sports and physical activities helping to lay the foundation for healthy, active lifestyles and quality learning experiences.
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