13.Ⅲ－Ⅴ族半導(dǎo)體制備的新方法.ppt

1、信息檢索與文獻(xiàn)閱讀 （化學(xué)0701-0702）,2010年3月26日,第一部分 化學(xué)專業(yè)基礎(chǔ)英語閱讀 （20學(xué)時(shí)） 第二部分 英文閱讀材料 （12學(xué)時(shí)） 第三部分 信息檢索 （16學(xué)時(shí)）,第一章 作為定量科學(xué)和物質(zhì)科學(xué)的化學(xué) 第二章 原子、分子和離子 第三章 氣態(tài) 第四章 熱化學(xué) 第五章 有機(jī)化合物和基團(tuán)的命名 第六章 無機(jī)化學(xué)、有機(jī)化學(xué)、物理化學(xué)、分 析化學(xué)化學(xué)術(shù)語,第一部分 化學(xué)專業(yè)基礎(chǔ)英語閱讀（20學(xué)時(shí)）,第二部分 英文閱讀材料（12學(xué)時(shí)）,第一章 松香酸度的標(biāo)準(zhǔn)測試方法 第二章 族半導(dǎo)體制備的新方法：InP納米晶 的超聲化學(xué)合成 第三章 專利說明書 第四章 銷售合同 第四章 分子離子材

2、料的計(jì)算機(jī)模擬 第四章 透射Laue法的X射線衍射,第三部分 信息檢索（16學(xué)時(shí)）,第一章 信息檢索基礎(chǔ) 第二章 超星圖書館 第三章 中國期刊網(wǎng) 第四章 維普 第五章 工程索引（Ei） 第六章 美國化學(xué)文摘（CA） 第七章 專利,教材和參考書： 1、魏高原， 化學(xué)專業(yè)基礎(chǔ)英語知識（I）（Introductory Chemistry Speciality English）， 北京大學(xué)出版社，2004。 2、 Reading Materials (自編講義) 。 3、 陳英，科技信息檢索（第二版），科學(xué)出版社，2005。 4、 萬錫仁， Information Retrieval and Rela

3、ted Reading Materials，（待出版）。 5、 美 Philip Ball 著，魏高原等注釋， 化學(xué)專業(yè)基礎(chǔ)英語（II）， 北京大學(xué)出版社，2001。,課堂教學(xué)內(nèi)容安排,第一節(jié)課 教學(xué)要求說明 詞匯預(yù)習(xí) 課文閱讀理解 第二節(jié)課 課文閱讀理解（續(xù)） 答疑 布置課后作業(yè) 詞匯和短文翻譯（書面練習(xí)）,一、教學(xué)要求 掌握： 期刊論文的書寫格式；有關(guān)專業(yè)詞匯， 科技英語的表達(dá)。 熟悉： 有關(guān)納米材料的基本知識。 了解： 納米材料的研究現(xiàn)狀。,二、 詞匯（New Words and Expressions）,semiconductor 半導(dǎo)體 sonochemical synthesis超

4、聲化學(xué)合成 nanocrystal 納米晶體 abstract摘要 diameter直徑 ultrasonic irradiation超聲輻射 yellow phosphorus 黃磷,semiconductor sonochemical synthesis nanocrystal abstract diameter ultrasonic irradiation yellow phosphorus,ethanol 乙醇 benzene苯 characterize表征 X-ray powder diffraction X射線粉末衍射 transmission electron microscop

5、e 透射電子顯微鏡,ethanol benzene characterize X-ray powder diffraction transmission electron microscope,electron diffraction pattern 電子衍射花樣 keyword 關(guān)鍵詞 introduction 引言 nanocrystalline inorganic semiconductor material 納米結(jié)晶的無機(jī)半導(dǎo)體材料,electron diffraction pattern keyword introduction nanocrystalline inorganic s

6、emiconductor material,markedly 明顯地 bulk 大塊物質(zhì) exploiting 開發(fā)，使用 device器件 characterization 表征 technological importance 技術(shù)上的重要性,markedly bulk exploiting device characterization technological importance,considerable 明顯的 explore 探索 synthetic route 合成路線 toxic 有毒的 precursor前驅(qū)物質(zhì) milder較溫和的 dehalosilylation 去

7、鹵硅烷化,considerable explore synthetic route toxic precursor milder dehalosilylation,subsequent隨后的，后來的 thermolysis熱分解作用 metathesis復(fù)分解 annealing 退火 tri-n-octylphosphine oxide TOPO,三辛基氧化膦 monodisperse 單分散的,subsequent thermolysis metathesis annealing tri-n-octylphosphine oxide monodisperse,fiber 纖維 solvot

8、hermal process 溶劑熱過程 cavitating bubble空化氣泡 amorphous metal 無定形金屬 alloy合金 carbide 碳化物 selenide硒化物,fiber solvothermal process cavitating bubble amorphous metal Alloy carbide selenide,deposition 沉積 to our knowledge 就我們所知 photoluminescence光致發(fā)光 electroluminescence電致發(fā)光 complex 復(fù)雜的 organometallic 有機(jī)金屬的 con

9、ventional慣例的, 常規(guī)的,deposition to our knowledge Photoluminescence Electroluminescence complex organometallic conventional,experimental 實(shí)驗(yàn)的 ultrasonic stirring超聲攪拌 reactor 反應(yīng)器 immerse沉浸 sealed 密封的 circulating water bath 循環(huán)水浴 precipitate 沉淀,experimental ultrasonic stirring reactor immerse sealed circula

10、ting water bath precipitate,vacuum 真空 X-ray diffractometer X射線衍射儀 radiation 輻射 transmission electron microscopy 透射電子顯微鏡方法（術(shù)） accelerating voltage 加速電壓 results and discussion結(jié)果和討論,vacuum X-ray diffractometer radiation transmission electron microscopy accelerating voltage result and discussion,mixture

11、混合物 derivative 衍生物 THF (=tetrahydrofuran) 四氫呋喃 ultrasonic wave超聲波 peak 峰 spacing 間距 corresponding to 對應(yīng)于,mixture derivative THF (=tetrahydrofuran) ultrasonic wave peak spacing corresponding to,reflection 反射 cubic立方的 broad peak 寬化的峰 peak width 峰寬 in agreement with 與一致 particle粒子 nanoparticle納米粒子,refl

12、ection cubic broad peak peak width in agreement with particle nanoparticle,heterogeneous異類的 homogeneous 均勻的，同類的 annealing region 退火區(qū)域 interfacial region 界面區(qū)域 induce 導(dǎo)致 yield 生產(chǎn)，產(chǎn)量 quenching rate 驟冷速率,heterogeneous homogeneous annealing region interfacial region induce yield quenching rate,involatile

13、 不揮發(fā)的 radical自由基, 游離基 sonification超聲處理 cavitation空化 oxidation氧化 reduction還原 dissolution 溶解,involatile radical sonification cavitation oxidation reduction dissolution,decomposition 分解 interparticle collision 粒子間碰撞 microjet微射流 shockwave沖擊波 well-dispersed 分散性好的 hinder阻礙, 打擾 viscosity 黏度（性）,decompositio

14、n interparticle collision microjet shockwave well-dispersed hinder viscosity,competition 競爭 particle growth粒子生長 nucleation 成核 diffusion擴(kuò)散 indium phosphide 磷化銦 migrate 遷移 conduct 進(jìn)行,competition particle growth nucleation diffusion indium phosphide migrate conduct,extend 延長 crystal growth晶體生長 dangling

15、 bond懸掛鍵 defect site 缺陷點(diǎn)位 stable穩(wěn)定的 extreme condition 極限條件 nonaqueous 非（無）水的,extend crystal growth dangling bond defect site stable extreme condition nonaqueous,non-oxygen environment 無氧環(huán)境 a trace of water 痕量的水 system 體系 on the contrary 相反 substitute 取代 UV/VIS absorption （Ultraviolet/ Visible absorp

16、tion ） 紫外可見吸收,non-oxygen environment a trace of water system on the contrary substitute UV/VIS absorption （Ultraviolet/ Visible absorption ）,absorption spectrum吸收光譜 band帶 surface state表面態(tài) stoichiometric 化學(xué)計(jì)量的 originating from 起源于,發(fā)生于 surface transition 表面躍遷 conclusion 結(jié)論,absorption spectrum band sur

17、face state stoichiometric originating from surface transition conclusion,summary摘要, 概要 maintain 維持，保持 inexpensive便宜的, 不貴重的 realize 實(shí)現(xiàn) transition metal phosphide 過渡金屬磷化物 acknowledgement 感謝，致謝 reference 參考文獻(xiàn),summary maintain inexpensive realize transition metal phosphide acknowledgement reference,三、課文

18、的閱讀理解,學(xué)生閱讀課文510分鐘，教師指定學(xué)生逐段朗讀課文，并翻譯成中文，教師及時(shí)評講。,A novel method for the preparation of III-V semiconductors：sonochemical synthesis of InP nanocrystals III-V族半導(dǎo)體制備的新方法：InP納米晶的超聲化學(xué)合成,1. What is the name of the Journal? 2. What is the title of this article ( or paper)?,3. What are bylines (authors and aff

19、iliation) ?,1. Abstract(摘要) 2. Text （正文） (1) Introduction（引言） (2) Experimental (or Computational method,)（實(shí)驗(yàn)或計(jì)算方法） (3) Results and Discussion（結(jié)果和討論） (4) Conclusion（結(jié)論） 3. Acknowledgments（致謝） 4. Appendix（附錄） 5. References（參考文獻(xiàn)）,Whats new for us for this paper? 2. What is the RTSCR route? 3. What are

20、prepared by the RTSCR route? 4. How did they characterize their products?,5. How to obtain the averaged particle size of the product? 6. Which solvents are used in their experiments? 7. Please describe the factors that play important roles in producing InP nanocrystals.,8. Is a small amount of water

21、 in the system helpful to the reaction?,1. Whats new for us for this paper?,The temperature used is to our knowledge the lowest at which crystalline InP has been obtained，and complex organometallic reaction or the toxic gas PH3 used in conventional routes to III-V semiconductors has been completely

22、avoided,2. What is the RTSCR route?,We call it the room temperature sonochemical reduction (RTSCR) route,4InCl3+12KBH4+P4 4InP+12KCl+12BH3+6H2,3. What are prepared by the RTSCR route?,lnP nanocrystals with diameter of 9 nm were successfully obtained,4. How did they characterize their products?,The p

23、roducts were characterized by X-ray powder diffraction, transmission electron microscope and electron diffraction pattern.,5. How to obtain the averaged particle size of the product?,The mean size of the InP nanocrystals was estimated to be 86 nm from the(1 l 1)peak width by Scherrers equation,6. Wh

24、ich solvents are used in their experiments?,ethanol and benzene,7. Please describe the factors that play important roles in producing InP nanocrystals?,The ultrasonic irradiation and the solvents are both important in the formation of the product,8. Is a small amount of water in the system helpful t

25、o the reaction?,Yes. When the reactant InCl34H20 was substituted by non-aqueous InCl3, with all other conditions kept constant，the yield of final product will markedly reduce.,A novel method for the preparation of III-V semiconductor has been provided in this paper,Abstract（摘要）,At room temperature，l

26、nP nanocrystals with diameter of 9 nm were successfully obtained under high-intensity ultrasonic irradiation for 4 h from the reaction of InCl34H2O，yellow phosphorus and KBH4 in the mixed solvents of ethanol and benzene,Changing some parameters can effectively control the size of the products and po

27、ssible explanations were offered,The products were characterized by X-ray powder diffraction, transmission electron microscope and electron diffraction pattern. The ultrasonic irradiation and the solvents are both important in the formation of the product,Keywords： Sonochemical synthesis； InP nanocr

28、ystals； Size control粒子大小控制,There is growing interest in nanocrystalline inorganic semiconductor materials，in large part due to the markedly different properties from their bulk counterpart副本, 極相似的人或物, 配對物and the promise of exploiting開拓, 開發(fā)these properties for making devices,1Introduction(引言),Althoug

29、h most studies in the field have focused on II-VI semiconductors(CdS，CdSe)1，2，the synthesis and characterization of III-V semiconductor nanocrystals such as GaAs3，and InP4-11 have also received renewed interest due to their technological importance,Over the last several years, there have been consid

30、erable efforts to explore synthetic routes for Ill-V semiconductor InP nanocrystals，with the goals of lowering processing temperature，avoiding complex reactions and toxic precursors and searching for milder溫和的preparation conditions,InP nanocrystals can be prepared by (dehalogenate脫鹵, 去掉鹵素) silylatio

31、n 硅烷化 ) dehalosilylation脫鹵硅烷化 of InCl3 and (Me3 Si)3P with subsequent thermolysis 熱分解(作用) at 650C 4 or 200-400C5,Solution phase metathesis復(fù)分解of lnCl3，and(NaK)3P can also be used to prepare InP nanocrystals，but annealing at higher temperature is required6,Recently InP with better quality has been mad

32、e by thermolysis reactions（熱解反應(yīng)） in tri-n-octylphosphine oxide(TOPO,三辛基氧化膦) by Micic et al7，which was further exploited開發(fā)by Alivisatos and coworkers8 to synthesize monodisperse 單分散(性)的and soluble InP nanocrystals,Crystalline InP fibers can be obtained at 111-203C，but extremely toxic PH3 was used in

33、the process9. Green and OBrien10 reported a direct and rapid synthesis of monodispersed InP quantum dots at 167C,Very recently，nanocrystalline InP was prepared by a solvothermal process (在非水溶劑中加壓制備納米晶的過程稱為溶劑熱過程)at a temperature of l 50C by our group11,Currently, the sonochemical method has been used

34、 extensively to generate novel materials with unusual properties，because the method causes the formation of particles of a much smaller size and higher surface area than those reported by other methods,Using extreme conditions inside a cavitating bubble空化氣泡內(nèi)，Suslick and coworkers have produced a var

35、iety of nanosized but often amorphous metals，alloy，and carbides1 2,Recently， sonochemical synthesis has been well explored to prepare selenides.硒化物This method can be used to prepare Cu(Ag，Pb)Se1 3，ZnSe14It also can be combined with electrochemical deposition to prepare CdSel 5 and PbSe 16,However，to

36、 our knowledge，there are no reports on the preparation of III-V semiconductors by ultrasonic irradiation,Here，we report a novel sonochemical method for the preparation of III-V semiconductor InP nanocrystals which are widely used due to their role in photoluminescence光致發(fā)光,electroluminescence電致發(fā)光devi

37、ces，etc,Nanocrystalline InP with an average particle size of 9 nm was obtained by this routeTo our knowledgethis is the first time that sonochemical synthesis was extended to prepare III-V semiconductors,The temperature used is to our knowledge the lowest at which crystalline InP has been obtained，a

38、nd complex organometallic reaction or the toxic gas PH3 used in conventional routes to III-V semiconductors has been completely avoided,2Experimental,In a typical process，InCl34H2O (0.55g，2.5mmol) and yellow phosphorus (0.62g, 5 mmol) were，respectively, dissolved in 75 ml ethanol and 25 ml benzene w

39、ith the aid of ultrasonic stirring for several minutes using a commercial ultrasonic cleaner.,Then the two solutions and KBH4硼氫化鉀(0.80 g，l5mmol)were placed in a 120 ml reactor，which was designed to ensure that the horn觸角 tip was immersed into the solution consistently to the same depth (10mm),The se

40、aled reactor was kept in circulating water bath to maintain the temperature of the bulk solution at 25土2C and was irradiated照射with high intensity ultrasound (model，R=l cm Ti horn，20 kHz，l 00 Wcm) for 4 h,Blackbrown precipitates were collected and washed with ethanol，dilute HCl(05 M)solution，and dist

41、illed water，and finally dried in vacuum at 60C for 4 h,The X-ray diffraction (XRD) patterns were obtained on a Japan Rigaku Dmax-A X-ray diffractometer with CuK radiation(=154178A)The transmission(透射) electron microscopy images were made on a Hitachi model H-800 with an accelerating voltage of 200 k

42、V.,3Results and discussion,The InP was prepared from the mixtures of InCl34H20，yellow phosphorus and KBH4 in the mixed solvents of ethanol and benzene under high-intensity ultrasonic irradiation at room temperature,In our process，KBH4 reduces（還原） the dissolved InCl34H2O to active indium element unde

43、r ultrasonic irradiationKBH4 and its derivatives have been used to prepare finely divided powders of metals and alloys by reducing metal salts in organic solvents such as THF（=tetrahydrofuran化四氫呋喃） and hydrocarbons 17,Ultrasonic waves that are intense enough to produce cavitation（空化作用） can drive hig

44、h energy for the reaction of phosphorus and newly produced indium to form InP nanocrystalsThe reaction can be formulated as follows：,We call it the room temperature sonochemical reduction (RTSCR) route,4InCl3+12KBH4+P4 4InP+12KCl+12BH3+6H2,The XRD pattern of sonochemically prepared InP is shown in F

45、ig1The nanocrystalline InP exhibited peaks with d spacings of 3.39，2.91，2.08，and 1.77 corresponding to the (1 1 1)，(2 0 0)，(2 2 0)，and(3 1 1) reflections of cubic lnP (JCPDS card no. 32452)，respectively,Fig 1 XRD pattern of sonochemically prepared InP nanocrystals,The broad peaks indicate that the c

46、rystal size is smallThe mean size of the InP nanocrystals was estimated to be 86 nm from the(1 l 1)peak width by Scherrers equation,The image of prepared InP (Fig. 2a) shows that the sample consists of a large number of relatively monodispersed dots，with an average diameter of about 8l0nm, which is

47、in good agreement with the XRD result,Energy dispersive X-ray analysis performed on these particles gave an In/P atomic ratio of 1.03:1, identical within experimental error to that from bulk chemical analysis,The XRD pattern(Fig1) and the selected area electron diffraction (ED) pattern(Fig2b) for so

48、no-chemically prepared InP reflect that these nanoparticles are well crystallized, which is markedly different from the general result that products prepared by high-intensity ultrasonic irradiation are often in amorphous form1 2,In our process，with the emergence, of newly indium reduced from the in

49、dium chloride，the reaction system become heterogeneous from the initial homogeneous systemThis heterogeneous process provides the possibility of annealing of the product,It has been known that three different regions are formed during heterogeneous sonochemical process 18: (a)the inner environment(g

50、as phase)of the collapsing bubble，where elevated temperature (several thousands of degrees) and pressure (hundreds of atmospheres) are produced；,(b) the interfacial region where the temperature is lower than in the gas phase region but still high enough to induce a sonochemical reaction；and (c) the

51、bulk solution，which is at ambient temperatures,Among the above mentioned three regions，it appears that the current sonochemical reaction occurs within the interfacial region，yielding nanocrystals，because of the not very high quenching rate experienced by the product,This is because phosphorus and in

52、dium are certainly involatile under normal conditions, but it might well dissociate or produce radicals under the extreme conditions of sonification 超聲處理 In this process，the ultrasonic irradiation plays an important role,Ultrasonic waves that are intense enough to produce cavitation can drive chemic

53、al reactions such as oxidation，reduction，dissolution，and decomposition 19.,When the experiments were made at room temperature with low intensity (such as produced by a commercial ultrasonic cleaner)or without ultrasonic irradiation，the XRD measurements show that no InP could be obtained even for eno

54、ugh time.,The high-intensity ultrasonic irradiation is necessarily fully responsible for those reactionsBecause of the effects of interparticle collision, microjet微射流 and shockwave沖擊波，the high-intensity ultrasonic irradiation is also helpful for the preparation of well-dispersed particles as shown i

55、n Fig.2a,In the processes of preparing InP，selecting ethanol and benzene as the mixed solvents is important to the formation of InP nanocrystalsIndium chloride and phosphorus can dissolve in ethanol and benzene，respectively,When using benzene as solvent，because of the insolubility of InCl34H20 in be

56、nzene，the In cannot be reduced by KBH4，not to mention the formation of lnPWhen using ethanol as solvent，only indium can be obtained in this process, in which the low solubility of phosphorus in ethanol hinders the formation of InP,We found that the ratio of added solvent had influence on the final p

57、article sizeAs Ref. 14reported the viscosity of system has important influence on the growth of the particles under high-intensity ultrasonic irradiation,In our process，by changing the volume ratio of added solvents，the size of the products can be effectively controlledWhen we added the ethanol and

58、benzene in the ratio of l:3, 1:1, and 3:1，the final particle sizes estimated from the Scherrer formula were 15, 12, and 9 nm，respectively,This influence is mainly related to the different viscosity of the reaction systemDuring the formation of the final product，the competition between particle growt

59、h and nucleation is partially controlled by diffusion,For highviscosity solutions，the rate of diffusion is low and the indium phosphide can form a new nucleus before they migrate to the surface of nuclei,The time of nucleation and length of the growth period of nuclei in different solution systems are not the same，giving particles with different sizes at the end of the growth processThe increasing of ethanol，which has higher viscosity than benzene，increase the viscosity of the reaction system,Therefore，the products size decrease with the increasing of the amount o