1、納米材料與納米科技13th May, 20091納 米1.什么是納米科學(xué)？2.納米材料及其特性3.納米技術(shù)的應(yīng)用 2What is Nanometer?A nanometer is about the width of six bonded carbon atoms, and approximately 40,000 are needed to equal the width of an average human hair. DNA (width) is 2 nmProteins range from 5 to 50 nmViruses range from 75 to 100 nmA vi

2、rus is 100 nmRed blood cells are 7,000 nm in diameter, and 2000 nm in heightWhite blood cells are 10,000 nm in diameter Bacteria range from 1,000 to 10,000 nmA hydrogen atom is 0.1 nmFullerenes (C60 / Buckyballs) are 1 nm Quantum Dots (of CdSe) are 8 -50 nm Dendrimers are 10 nmNanoparticles range fr

3、om 1 to 100 nm3Importance“One nanometer is a magical point on the dimensional scale. Nanostructures are at the confluence of the smallest of the human-made devices and the largest molecules of living things. Nanoscale science and engineering here refer to the fundamental understanding and resulting

4、technological advances arising from the exploitation of new physical, chemical and biological properties of systems that are intermediate in size, between isolated atoms and molecules and bulk materials, where the transitional properties between the two limits can be controlled.”M.C. Roco (National

5、Science Foundation), 2001.4Theres Plenty of Room at the Bottomby Richard P. Feynman December 29th 1959 年，諾貝爾獎(jiǎng)獲得者、理論物理學(xué)家理查得費(fèi)因曼教授在加州理工大學(xué)發(fā)表了題為在底部還有很大空間的演講。在費(fèi)因曼看來，人類社會(huì)目前的生產(chǎn)方式，總是“從上而下(top-down Manufacturing)”的，他提出：為什么我們不可以從單個(gè)分子、甚至原子開始出發(fā)進(jìn)行組裝 (bottom-up manufacturing) ，達(dá)到我們的要求？物理學(xué)的規(guī)律不排除一個(gè)原子一個(gè)原子制造物品的可能?！保{米

6、科學(xué)的開山之作） 5Nanoscience Study of fundamental principles of molecules and structures with at least one dimension roughly between 1 and 100 nm. Nanotechnology- sometimes shortened to nanotech, refers to a field of applied science whose theme is the control of matter on an atomic and molecular scale. Gen

7、erally nanotechnology deals with structures 100 nanometers or smaller, and involves developing materials or devices within that size.Nanostructures Smallest solid things it is possible to make.67“Nanotechnology is likely to be particularly important in the developing world, because it involves littl

8、e labour, land or maintenance; it is highly productive and inexpensive; and it requires only modest amounts of materials and energy” UN Millennium Project. “Nanoscience and technology will change the nature of almost every human-made object in the 21st century” - M.C. Roco, R.S. Williams, P. Alivisa

9、tos, 1999 the National Science and Technology Council “Just waitthe 21st century is going to be incredible. We are about to be able to build things that work on the smallest possible length scales, atom by atom. These nanothings will revolutionize industries and our lives” - Richard Smalley, 1999 (1

10、996 noble prize in chemistry)The convergence of nanotechnology with information technology, biology and social sciences will reinvigorate discoveries and innovation in many areas of the economy. - George W. Bush, President of the United States7Macroscale vs. Nanoscale Gold 8Nano-sizing Causes Change

11、s In Melting point:Macroscale vs. Nanoscale Gold Nanoscale Materials in Chemistry, K. J. Klabunde, ed., Wiley, 2001, Chapter 8.9一、C60近年來，科學(xué)家們發(fā)現(xiàn)，除金剛石、石墨外，還有一些新的以單質(zhì)形式存在的碳。其中發(fā)現(xiàn)較早并已在研究中取得重要進(jìn)展的是C60分子。C60分子是一種由60個(gè)碳原子構(gòu)成的分子，它形似足球，因此又名足球烯。10Nanoscience is a subject defined by its dimension. Sometimes its fun

12、 to play with that a little. If a buckyball was as big as a football, a football would be as big as the earth! These flourinated fullerenes come from the work of Roger Taylor and Adam Darwich 1112制作過程足球烯是美國休斯頓賴斯大學(xué)的克羅脫和史沫萊等人于1985年提出的。他們用大功率激光束轟擊石墨使其氣化，用1MPa壓強(qiáng)的氦氣產(chǎn)生超聲波，使被激光束氣化的碳原子通過一個(gè)小噴嘴進(jìn)入真空膨脹，并迅速冷卻形成新

13、的碳原子，從而得到了C60。13Fullerene Science1985: C60-discovered (Nature 318, 162) 1990: C60-macroscopic scale synthesis (Nature 347, 354)1991: Carbon nanotubes-discovered (Nature 354, 56)1996: Noble prize for C601415C60的應(yīng)用氣體的貯存在控制溫度和壓力的條件下，可以簡單地用C60和氫氣制成C60的氫化物，它在常溫下非常穩(wěn)定，而在80 215 時(shí)，C60的氫化物便釋放出氫氣，留下純的C60，它可以被1

14、00%地回收，并被用來重新制備C60的氫化物。與金屬或其合金的貯氫材料相比，用C60貯存氫氣具有價(jià)格較低的優(yōu)點(diǎn)，而且C60比金屬及其合金要輕。C60的應(yīng)用16因此，相同質(zhì)量的材料，C60所貯存的氫氣比金屬或其合金要多。C60不但可以貯存氫氣，還可以用來貯存氧氣。與高壓鋼瓶貯氧相比，高壓鋼瓶的壓力為3.9106 Pa，屬于高壓貯氧法，而C60貯氧的壓力只有2.3105 Pa，屬于低壓貯氧法。利用C60在低壓下大量貯存氧氣對(duì)于醫(yī)療部門、軍事部門乃至商業(yè)部門都會(huì)有很多用途。17有感覺功能的傳感器由于用C60薄膜做基質(zhì)材料可以制成手指狀組合型的電容器，用它來制成的化學(xué)傳感器具有比傳統(tǒng)的傳感器尺寸小、簡

15、單、可再生和價(jià)格低等優(yōu)點(diǎn)，可能成為傳感器中頗具吸引力的一種候選產(chǎn)品。18此外提高金屬硬度應(yīng)用于新型催化劑對(duì)光的限制性可應(yīng)用于對(duì)人的眼睛的保護(hù)對(duì)癌細(xì)胞殺傷抑制人體免疫缺損蛋白酶的活性充當(dāng)水溶性抗氧劑 等等19納米材料納米材料: 在納米量級(jí)(1100nm)內(nèi)調(diào)控物質(zhì)結(jié)構(gòu)制成的具有特異性能的新材料四大特點(diǎn): 尺寸小、比表面積大、表面能高、表面原子比例大四大效應(yīng): 小尺寸效應(yīng)、量子尺寸效應(yīng)、宏觀量子隧道效應(yīng)、表面效應(yīng)納米材料特性取決于制備方法20納米材料應(yīng)用21環(huán)境：處理汽車尾氣含鉛汽油中的鉛很容易通過血液長期蓄積于人的肝、腎、脾、肺和大腦中，從而導(dǎo)致人的智能發(fā)育障礙和血色素制造障礙等后果。汽車尾氣的

16、處理：加入納米級(jí)的復(fù)合稀土氧化物后，對(duì)尾氣的凈化特別明顯，尾氣中的CO、NOx幾乎完全轉(zhuǎn)化。22水處理特種半導(dǎo)體納米材料使海水淡化；納米TiO2可以用來降解有機(jī)磷，降解毛紡染整廢水，降解石油 23能源：儲(chǔ)氫碳納米管是直徑非常細(xì)的中空管狀納米材料，它能夠大量地吸附氫氣，成為許多個(gè)“納米鋼瓶” 。研究表明，約2/3的氫氣能夠在常溫常壓下從碳納米管中釋放出來。據(jù)預(yù)測，到2010年，就可以生產(chǎn)出氫氣汽車，只需攜帶1.5升左右的儲(chǔ)氫納米碳管，即可行駛500km。24納米碳管25防彈衣因納米碳管既輕又強(qiáng)度極高，是鋼的10100倍，用它來作防彈衣就像用羽絨做成的防寒服一樣，既可折來疊去，又能抵御強(qiáng)大的子彈的

17、沖擊力。26納米泵人造紅細(xì)胞它比體內(nèi)血液中的紅細(xì)胞要多攜帶200多倍的氧氣。血液形態(tài)圖 27靶向給藥美國麻省理工學(xué)院的研究人員研究一種只有20nm的藥物炸彈和包含了1000個(gè)納米藥包的微型芯片；在固定的DNA鏈上連接上殺癌的藥物膠囊，放到病人血液和組織內(nèi)，一遇上癌細(xì)胞的DNA時(shí)，DNA鏈就與癌細(xì)胞的DNA結(jié)合，這時(shí)藥物開關(guān)受觸發(fā)而開放，藥物便釋放出來，殺滅癌細(xì)胞；28 生物醫(yī)藥：納米清潔工科學(xué)家設(shè)想制造出負(fù)責(zé)清掃血管的納米機(jī)器人（清潔工），專門負(fù)責(zé)清掃血管壁上的膽固醇、凝血等沉積物，以預(yù)防腦血栓等心血管??；同時(shí)也可以制作出清掃體內(nèi)癌細(xì)胞的機(jī)器人。29太空云梯堅(jiān)韌的碳纖維，其密度是鋼的1/6，強(qiáng)

18、度為鋼的10100倍，重量則只有鋼的1/4。將納米碳管做成太空升降機(jī)的纜繩，由于它的強(qiáng)度高、重量輕，即使是從太空下垂到地面，它也完全可以承受自身的重量而不會(huì)斷開，它是目前唯一可作為太空云梯的理想材料。30日常生活納米TiO2：在光照條件下，會(huì)產(chǎn)生具有非常強(qiáng)的氧化能力的空穴，從而將附在表面上的有機(jī)物、細(xì)菌及其它灰塵分解掉，直至生成CO2和H2O。殺菌、除味：由于納米ZnO具有大的比表面積，可以很快地吸收并分解臭氣，同時(shí)還能有效地殺菌。對(duì)黃色葡萄球菌和大腸桿菌的殺菌率高達(dá)95%以上?？咕{米服裝：不用清洗信不信由你31軍事吸波：納米ZnO對(duì)雷達(dá)電磁波具有很強(qiáng)的吸收能力，所以可以做隱形飛機(jī)的重要涂料

19、。322005年10月20日?qǐng)?bào)道， 目前美國Nice大學(xué)的科學(xué)家研制出世界第一輛單分子納米汽車。該汽車在顯微鏡下可見的金屬道路上行駛。車輪是球型的，由包含60個(gè)原子的單質(zhì)碳構(gòu)成。整輛汽車對(duì)角線的長度僅為34納米，比單股的DNA稍寬。相比而言，人一根頭發(fā)的直徑大約是80，000納米。納米汽車33納米管收音機(jī)2007 年，美國加利福尼亞大學(xué)伯克利分校的物理學(xué)家亞歷克斯策特爾(Alex Zettl) 。在該碳納米管收音機(jī)中，碳納米管承擔(dān)了收音機(jī)的天線、調(diào)諧器、放大器和解調(diào)器等諸多部件的功能。如圖1所示，納米收音機(jī)的碳納米管被置于真空管中，并將一端固定在電池的負(fù)極上。碳納米管的另一端（即自由端）和電池

20、正極之間留有納米量級(jí)的間隙。如果電極間的電壓足夠高，正極能將碳納米管自由端的電子奪過來。當(dāng)廣播電臺(tái)的無線電信號(hào)經(jīng)過該碳納米管收音機(jī)時(shí)，其產(chǎn)生的電場將不斷“推”和“拉”納米管的自由端，也就是碳納米管隨無線電信號(hào)發(fā)生共振，利用這種共振現(xiàn)象及回路中相應(yīng)的電流變化就可以探測到無線電信號(hào)。這里，回路中受無線電信號(hào)感應(yīng)得到的高頻交變電流信號(hào)后經(jīng)碳納米管“調(diào)諧”、“放大”和“解調(diào)”后，便會(huì)轉(zhuǎn)化為攜帶聲音信息的低頻信號(hào)，進(jìn)而，通過喇叭等播出聲音。 34萬能關(guān)節(jié)Name: Universal JointDesigner: Mark Sims, based on a 1992 design by K. Eric

21、Drexler and Ralph MerkleDate: May 25, 2006Number of components: 4 (which form a single covalent structure)Number of atoms: 3,846Width: 3.8 nmHeight: 3.8 nmLength: 6.4 nm (not including shafts) 35世界最小的納米電動(dòng)機(jī)：以碳納米管為軸，金片為葉，在電流驅(qū)動(dòng)下轉(zhuǎn)動(dòng) 36ATP分子馬達(dá) 該生物馬達(dá)由腺苷三磷酸酶ATP吸附在鎳螺旋槳周圍，并給主軸提供能量37利用碳納米管制造出一種奇妙的納米秤，這種秤竟然可以稱出

22、單個(gè)原子的重量。之所以選用碳納米管來作為制作納米秤的材料，是因?yàn)樘技{米管中間是空的，而且質(zhì)量非常輕，對(duì)原子的振動(dòng)非常敏感，這樣可以更準(zhǔn)確的“秤”出原子的重量 。不過它并不是利用杠桿原理來稱量原子的重量。這種納米秤實(shí)際上是一個(gè)懸臂，類似于跳水運(yùn)動(dòng)員使用的跳板，長約250納米，一頭固定在一個(gè)電極上，另一頭則不固定。當(dāng)一個(gè)原子落下掉在這個(gè)懸臂上，原子的重量會(huì)引起懸臂進(jìn)行振動(dòng)。這就像跳水板一樣，跳水運(yùn)動(dòng)員的體重不同，跳水板的振動(dòng)頻率和幅度也會(huì)有相應(yīng)的變化。然后他們利用振動(dòng)頻率的差異來測算出原子的重量。 納米秤3839nano guitar playable and coloredA nanoguita

23、r, devised at Cornell years ago, has been played for the first time by shooting laser light at the silicon strings. A newer version of the guitar, shown above, twangs at a frequency of 40 megahertz, some 17 octaves (or a factor of 130,000) higher than a normal guitar. Electron-microscope image of th

24、e worlds smallest guitar. Its length is 10 micrometers (10 millionths of a meter).Thats about the size of a red blood cell and about 1/20th the width of a single human hair. Its strings have a width of about 50 nanometers (the size of approximately 100 atoms). If you were to pluck the tiny strings t

25、hey would produce a high-pitched sound at the inaudible frequency of approximately 10 megahertz. Made by Cornell researchers with a single silicon crystal using the techniques of high voltage electron beam lithography, this tiny guitar is a fun example of nanotechnology.Many of the same techniques a

26、re applied by scientists building machines and devices on the nanometer scaleto perform useful technological functions and study submicroscopic processes. 40納米上的藝術(shù)41納米尺度的世界名畫！ （a）原畫（b）納米摹本 新加坡國立大學(xué)科學(xué)家利用離子束寫入技術(shù)，把十九世紀(jì)英國畫家威廉布萊克的經(jīng)典名畫轉(zhuǎn)移到了可以精細(xì)調(diào)節(jié)的納米晶體上?？茖W(xué)家稱之為“量子藝術(shù)”。精度為100微米，細(xì)節(jié)尺寸達(dá)到納米量級(jí)。42誘人的納米棒棒糖這是一張電子顯微鏡照片，

27、顯示的是一個(gè)微觀的納米結(jié)構(gòu)，該結(jié)構(gòu)酷似一個(gè)誘人的棒棒糖。 在兩個(gè)鎳電極間的一根硅納米線。右邊，納米線連著一個(gè)小的納米鎳金屬球，看起來就象是個(gè)棒棒糖。所以叫它納米棒棒糖。此圖由日立S-4700場發(fā)射掃描電鏡拍攝。43美國NASA用分子動(dòng)力學(xué)模擬的分子齒輪（視頻） （a）分子齒輪 （b）分子齒輪溫度及角速度隨時(shí)間的變化44搭建在一根頭發(fā)上的體育場館 采用離子束加工技術(shù)，日本學(xué)者Shinji MATSUI在一根頭發(fā)上成功搭建了體育場。45 日本學(xué)者2006年利用FIB-CVD 技術(shù)制備的納米LRC電子電路。46nanocupProfessor Shinji Matsuis research grou

28、p at the Himeji Institute of Technology (HIT) and Seiko Instruments Inc. (SII), have made the worlds smallest wine glass. Using highly advanced manufacturing techniques that can produce three dimensional (3D) objects at the nanometer scale, researchers built the glass from carbon with an external di

29、ameter of only 2,750 nanometers (nm), approximately 200,000 times smaller than a normal sized glass. 47nanocup48Nano flowers49NASA科研人員制備的Si納米結(jié)構(gòu) 50納米向日葵（美國康納爾大學(xué)科技人員制備的葸氫醌二乙酸酯納米結(jié)構(gòu)） 51522006， made from zinc oxide by Yujin Chen and colleagues at Harbin Engineering University，F(xiàn)or alcohol detection53超疏水 S

30、nO2 nanoflowers54a）硫化鎘納米花 （CVD方法）美國能源部：Sandia國家實(shí)驗(yàn)室55Carbon上生長的銻納米草 (新西蘭科學(xué)家的AFM照片)56Si上生長的硫化鉬納米錐 (新加坡國立大學(xué)電鏡照片) 57北京大學(xué)納米中心的學(xué)者通過AFM針尖對(duì)基質(zhì)Au-Pa合金上的機(jī)械刻蝕，書寫了世界上最小的唐詩（10微米10微米）5859DNA 美洲地圖60Nanoman was created by focussed electron beam deposition on the tip of an STM - an illustration of 3D nanostructure fa

31、brication with a precision of 10nm. 61“小人嘴臉” 這時(shí)美國加利福尼亞技術(shù)學(xué)院的科學(xué)家繪制的世界上最小的“小人”笑臉。使用的材質(zhì)為DNA分子鏈，笑臉的尺寸為僅為幾百納米。62原子小人這是科學(xué)家通過原子力顯微鏡操縱28 個(gè)碳原子在鉑表面上拼成的小人，28個(gè)原子組成的“人”.63Nano toilet在實(shí)驗(yàn)室里化學(xué)家一不小心在Si表面生成了上述“坐便器”形狀的納米結(jié)構(gòu)，這應(yīng)該是世界上最小的“坐便器”了，您需要電子顯微鏡才能看得到。64Micro-bull fabricated by FIB65分子的藝術(shù) 螞蚱酮 它是從一種不能飛的蝗蟲Romalea micro

32、ptera用于防御的分泌物中提取的.科學(xué)家們?cè)谔镆袄镄量嗟卮涷?、并惹惱它們，再從它們身上“擠奶”得到這種物質(zhì)，專注的科學(xué)家太累了而不想辛苦的對(duì)它系統(tǒng)命名，所以他們使用了這個(gè)有創(chuàng)意的名字螞蚱酮。 66納米莆田分子 這涉及到如何合成擬人的分子（anthropomorphic molecules），即分子結(jié)構(gòu)看起來就像是一個(gè)人。它們（指分子）有著不同的形式，但基本的形式被稱為“納米孩子”（NanoKid），從這里出發(fā)，其他不同形式的分子可以被合成，例如“納米運(yùn)動(dòng)員”（NanoAthlete）和“納米面包師”（NanoBaker）。 國王運(yùn)動(dòng)員面包師學(xué)者廚師特種部隊(duì)隊(duì)員小丑德克薩斯人朝圣者67企鵝酮

33、由于它分子的二維結(jié)構(gòu)式類似一只企鵝，所以被命名為“企鵝酮”（Penguinone），但是這種效果在三維模型中卻失去了。它的系統(tǒng)命名應(yīng)該是 3,4,4,5-tetramethylcyclohexa-2,5-dienone. 6869納米材料的常見制備方法70The scanning electron microscopic image of a 3D macroporous material that was fabricated by infiltrating a 3D opaline lattice of silica spheres with a hexane solution conta

34、ining buckyballs. Note that the porous features underneath were also visible through the pores on the surface of the membrane.Typical fabrication模板合成71納米芯殼結(jié)構(gòu)The scanning electron microscopic image of a 3D crystalline lattice assembled from AuSiO2 core-shell colloids. The gold cores were 50 nm in dia

35、meter and the silica shells were 120 nm in thickness. 72氧化鋁模板DpDc73Fabricated in 0.3 M oxalic acid solution, 40V, 2 oCTypical SEM images of as-prepared AAO templates74SEM images of Co nanowires fabricated by pulse DC electrodeposition(a)(b)(c)(d)75以粒徑為6微米的金紅石相氧化鈦為原料，制備無定形氧化鈦納米粉體的過程：TiO2粗粉水洗20M,NaOH,

36、200oC無定形氧化鈦300oC熱處理0.5h水熱法76無定形氧化鈦0.2M HCl1.0M HCl水洗水洗銳鈦礦相金紅石相(a): 無定形氧化鈦產(chǎn)物, (b): 銳鈦礦相氧化鈦產(chǎn)物, （c): 金紅石相氧化鈦產(chǎn)物.7720M,NaOH130oC-170oCTiO2微米粉體水洗納米管20M,NaOH200oC-250oC水洗納米絲78Schematic illustration of vapor-liquid-solid nanowire growth mechanism including three stages (I) alloying, (II) nucleation, and (II

37、I) axial growth.CVD制備納米線79(a) SEM image of ZnO nanowires synthesized via the VLS mechanism (b) TEM images of the single-crystalline ZnO nanowires.80SEM (a, c) and cross sectional TEM (b) images of SnO2 nanobelts obtained by evaporation and condensation of SnO at 1000 oC.81ZnO nanowire arrays on sapp

38、hire substrate. Huang M., Mao S., Feick H., Yan H., Wu Y., Kind H., Weber E., Russo R., and Yang P., Room-temperature ultraviolet nanowire nanolasers, Science 292(2001) pp.1897-189982Site-selective growth of ZnO nanowire arrays on a-plane sapphire substrates. The pattern of nanowire array is defined

39、 by the initial Au thin film pattern fabricated by photolithography.Science 292(2001) pp.1897-189983STEM image of two nanowires in bright field mode. The scale bar is 500 nm. (b) Line pro EDS signal from Si and Ge components along the nanowire growth axis. Wu Y., Fan R. and Yang P., Block-by-Block G

40、rowth of Single-Crystalline Si/SiGe Superlattice Nanowires, Nano Lett. 2(2002) pp.83-86.84Electrical field induced nanowire alignment represents another powerful assembly technique. Lieber et al. have fabricated metal electrode arrays on which bias is applied to generate strong electrical filed to a

41、lign Si and InP nanowires dispersed in between the electrodes(b). Typical SEM images of crossed arrays of InP nanowires obtained in a two-step assembly process with orthogonal flow directions for the sequential steps. Flow directions are highlighted by arrows in the images. The scale bar corresponds

42、 to 2 m.The microchannels are formed between a flat Si/glass substrate. A droplet of the wire solution/suspension was placed at the open end of the microchannels; the liquid fills the channels under capillary effect. After the evaporation of the solvent， wires were aligned along the edges of the microchannels。（a）SEM image of the aligned Mo3Se3 - molecular wire bundles on Si wafer. Inset shows the cross-junction formed through multiple layer alignment process. 納米線的排列85The melting starts from two ends at around 650 o