NGHIÊN CỨU CHẾ TẠO VÀ TÍNH CHẤT QUANG CỦA CHẤM LƯỢNG TỬ BÁN DẪN HỢP CHẤT BA NGUYÊN TỐ I-III-VI2 (CuInS2)

Header Page of 89 B GIO DC V éO TO VIN HN LM KH & CN VIT NAM VIN KHOA HC VT LIU NGUYN TH MINH THY NGHIấN CU CH TO V TNH CHT QUANG CA CHM LNG T BN DN HP CHT BA NGUYấN T I-III-VI2 (CuInS2) LUN N TIN S KHOA HC VT LIU H NI - 2014 Footer Page of 89 Header Page of 89 B GIO DC V éO TO VIN HN LM KH & CN VIT NAM VIN KHOA HC VT LIU NGUYN TH MINH THY NGHIấN CU CH TO V TNH CHT QUANG CA CHM LNG T BN DN HP CHT BA NGUYấN T I-III-VI2 (CuInS2) Chuyờn ngnh: Vt liu Quang hc, Quang in t v Quang t Mó s: 62 44 50 05 LUN N TIN S KHOA HC VT LIU NGI HNG DN KHOA HC: GS TS NGUYN QUANG LIấM PGS TS V DON MIấN H NI- 2014 Footer Page of 89 Header Page of 89 LI CM N Li u tiờn, tụi xin by t lũng kớnh trng v bit n sõu sc ti hai ngi thy hng dn l GS TS Nguyn Quang Liờm v PGS TS V Doón Miờn, nhng ngi thy ó nh hng cho tụi t khoa hc, tn tỡnh ch bo v to rt nhiu thun li cho tụi sut quỏ trỡnh thc hin lun ỏn Tụi xin chõn thnh cm n cỏc cỏn b v nghiờn cu sinh phũng Vt liu Quang in t (TS Trn Th Kim Chi, TS ng Th Diu Thỳy, ThS Trn Th Thng Huyn, CN Lờ Vn Long, TS Phm Th Thy,) - nhng ngi ó luụn giỳp , khớch l, ng viờn tụi sut thi gian lm lun ỏn Tụi xin chõn thnh cm n cỏc cỏn b Phũng Thớ nghim Trng im Quc gia v vt liu v linh kin in t, Vin Khoa hc vt liu ó giỳp tụi thc hin phộp o nh vi hỡnh thỏi, ph nhiu x tia X v ph tỏn x Raman Tụi xin trõn trng cm n B phn o to sau i hc, Vin Khoa hc Vt liu, ó to iu kin thun li cho tụi lm lun ỏn nghiờn cu sinh Tụi xin gi li cm n ti cỏc cỏn b, ging viờn, c bit l Ban lónh o khoa Giỏo dc THCS v Ban lónh o Trng i hc S phm, i hc Thỏi Nguyờn ó ng viờn, to iu kin thun li cho tụi tụi thc hin tt lun ỏn Tụi xin trõn trng cm n B Giỏo dc v o to, Vin Khoa hc vt liu, ó to iu kin thun li cho tụi lm lun ỏn nghiờn cu sinh Nhõn dp ny tụi xin dnh nhng tỡnh cm sõu sc nht ti nhng ngi thõn gia ỡnh: M, anh, ch, em ó chia s nhng khú khn, thụng cm v ng viờn, h tr tụi Footer Page of 89 Header Page of 89 Cui cựng tụi xin dnh nhng tỡnh cm c bit v bit n ca mỡnh ti chng v cỏc con, bng tỡnh yờu, s cm thụng, quan tõm v chia s, ó cho tụi ngh lc, to ng lc cho tụi thc hin thnh cụng lun ỏn H Ni, ngy thỏng nm 2014 Tỏc gi, Nguyn Th Minh Thy Footer Page of 89 Header Page of 89 Li cam oan Tụi xin cam oan õy l cụng trỡnh nghiờn cu ca riờng tụi di s hng dn ca GS TS Nguyn Quang Liờm v PGS TS V Doón Miờn Cỏc s liu v kt qu lun ỏn l trung thc v cha c cụng b bt c cụng trỡnh no khỏc Tỏc gi lun ỏn Nguyn Th Minh Thy Footer Page of 89 Header Page of 89 MC LC Danh mc cỏc ch vit tt v ký hiu Danh mc cỏc bng Danh mc cỏc hỡnh v M U Chng 1: Tng quan v vt liu nanụ v bỏn dn hp cht I-III-VI2 cu trỳc nanụ 1.1 Mt s hiu ng c bit ca vt liu nanụ 1.1.1 Hiu ng giam gi lng t 1.1.2 Hiu ng b mt 10 1.2 Tớnh cht quang ca vt liu bỏn dn cu trỳc nanụ 12 1.2.1 Tớnh cht hp th 13 1.2.2 Tớnh cht phỏt quang 16 1.2.2.1 Mt s c ch phỏt quang 16 1.2.2.2 Tớnh cht phỏt quang ph thuc nhit 18 1.3 Vt liu bỏn dn hp cht nguyờn I-III-VI2 cu trỳc nanụ 19 Kt lun chng 27 Chng 2: Cỏc phng phỏp thc nghim s dng lun ỏn 29 2.1 Phng phỏp ch to chm lng t 29 2.1.1 ng hc quỏ trỡnh to mm 30 2.1.2 ng hc quỏ trỡnh phỏt trin tinh th 33 2.1.3 Phng phỏp phun núng (hot-injection) 35 2.1.4 Phng phỏp gia nhit (heating-up) 36 2.1.5 Phng phỏp thu nhit (hydrothermal) 37 2.2 Mt s phng phỏp nghiờn cu vi hỡnh thỏi v cu trỳc ca vt liu 2.2.1 Phng phỏp nghiờn cu vi hỡnh thỏi 38 2.2.1.1 Kớnh hin vi in t quột (SEM) 38 2.2.1.2 Kớnh hin vi in t truyn qua (TEM) 39 2.2.2 Phng phỏp nghiờn cu cu trỳc Footer Page of 89 38 40 Header Page of 89 2.2.2.1 Phng phỏp nhiu x tia X 40 2.2.2.2 Phng phỏp ph tỏn x Raman 42 2.3 Mt s phng phỏp nghiờn cu tớnh cht quang ca vt liu 44 2.3.1 Phng phỏp ph hp th 44 2.3.2 Phng phỏp ph hunh quang 45 2.3.2.1 Phng phỏp ph hunh quang dng 46 2.3.2.2 Phng phỏp ph hunh quang phõn gii thi gian 47 Kt lun chng 48 Chng 3: Cụng ngh ch to, vi hỡnh thỏi v cu trỳc ca chm lng t 50 CuInS2, CuIn(Zn)S2 v CuInS2/ZnS 3.1 Chm lng t CuInS2 v CuInS2/ZnS cu trỳc lừi/v 3.1.1 Ch to chm lng t CuInS2 v lừi CuInS2/ v ZnS 3.1.1.1 Ch to chm lng t CuInS2 lừi bng phng phỏp gia nhit 50 50 50 3.1.1.2 Ch to chm lng t CuInS2 lừi bng phng phỏp phun núng 57 3.1.1.3 Ch to chm lng t CuInS2 bng phng phỏp thu nhit 58 3.1.1.4 Bc v cỏc chm lng t CuInS2 vi ZnS 62 3.1.2 nh vi hỡnh thỏi v cu trỳc ca chm lng t CuInS2 v CuInS2/ZnS 66 3.1.2.1 nh vi hỡnh thỏi ca chm lng t CuInS2 v CuInS2/ZnS 66 3.1.2.2 Cu trỳc ca chm lng t CuInS2 v CuInS2/ZnS 68 3.2 Chm lng t bỏn dn hp cht CuIn(Zn)S2 v CuIn(Zn)S2/ZnS 74 3.2.1 Ch to cỏc chm lng t hp cht CuIn(Zn)S2 v CuIn(Zn)S2/ZnS 74 3.2.1.1 Ch to cỏc chm lng t hp cht CuIn(Zn)S2 lừi 74 3.2.1.2 Bc v ZnS cho chm lng t hp cht CuIn(Zn)S2 76 3.2.1.3 Ch to cỏc chm lng t CuIn(Zn)S2 v CuIn(Zn)S2/ZnS Footer Page of 89 mụi trng nc 76 3.2.2 nh vi hỡnh thỏi v cu trỳc ca chm lng t hp cht CuIn(Zn)S2 78 3.2.2.1 nh vi hỡnh thỏi ca chm lng t hp cht CuIn(Zn)S2 78 3.2.2.2 Cu trỳc ca chm lng t hp cht CuIn(Zn)S2 80 Header Page of 89 3.3 Chm lng t hp cht CuIn(Al)S2 82 3.3.1 Ch to cỏc chm lng t hp cht CuIn(Al)S2 82 3.3.2 Cu trỳc ca cỏc chm lng t hp cht CuIn(Al)S2 85 Kt lun chng 86 Chng 4: Tớnh cht quang ca chm lng t CuInS2 v CuIn(Zn)S2 87 4.1 Hiu ng giam gi lng t 88 4.2 nh hng ca t l cỏc tin cht Cu:In 94 4.3 Th ng hoỏ b mt chm lng t CuInS2 bng lp vt liu v ZnS 95 4.4 Hunh quang tỏi hp in t-l trng cỏc cp ụno-axộpto 99 4.5 Vai trũ ca Zn s hỡnh thnh v phỏt trin cỏc chm lng t lừi hp cht CuIn(Zn)S2 104 4.6 Vai trũ ca Al s iu chnh nng lng vựng cm v nng lng tỏi hp phỏt quang chm lng t CuIn(Al)S2 110 4.7 Tớnh cht hp th v hunh quang ph thuc nhit ca chm lng t CuIn(Zn)S2 112 4.8 S truyn nng lng gia cỏc chm lng t lừi hp cht CuIn(Zn)S2 117 Kt lun chng 119 KT LUN 121 DANH MC CC CễNG TRèNH CễNG B 123 TI LIU THAM KHO 124 Footer Page of 89 Header Page of 89 DANH MC CC BNG STT Trang Bng 1.1 S nguyờn t v nng lng b mt ca ht nano cu to t nguyờn t ging Bng 1.2 11 Tớnh cht hunh quang ca cỏc tinh th nanụ thuc nhúm II-VI v I-III-VI [32] 24 74 Bng 3.1 Cỏc mode dao ng c trng ca CIS (CIS ch to diesel) Bng 3.2 Cỏc mode dao ng c trng ca CIS v CIZS (Cu:In:S = 0,8:1:2; In/MPA = 1/70; to mm nhit phũng; thi gian v nhit phỏt trin tinh th 60 phỳt, 120 oC Bng 4.1 nh hp th, hunh quang ca chm lng t CIZS ch to diesel theo t l phõn t Zn:(Cu+In) Footer Page of 89 82 106 Header Page 10 of 89 DANH MC HèNH V STT Trang Hỡnh 1.1 Cu trỳc vựng nng lng ca tinh th khi, chm lng t v phõn t Hỡnh 1.2 Mt trng thỏi ca in t t cỏc h bỏn dn 3D, ging lng t 2D, dõy lng t 1D v chm lng t 0D Hỡnh 1.3 Mt s chuyn di in t hp th quang: 1- Hp th riờng; 2-Hp th exciton; 3a, 3b- Hp th bi cỏc ht ti in t do; 4a, 4b- Hp th cht - vựng gn; 4c, 4dHp th cht - vựng xa; 5- Hp th gia cỏc cht 14 Hỡnh 1.4 Cỏc dng chuyn mc vựng-vựng bỏn dn 15 Hỡnh 1.5 Cỏc quỏ trỡnh hp th v phỏt quang tinh th 17 Hỡnh 1.6 Cu trỳc v nng lng vựng cm ca h bỏn dn hp cht nguyờn I-III-VI2 20 21 Hỡnh 1.7 Cu trỳc mng lp phng ca ZnS (a) v mng tinh th CuInS2 (b) Hỡnh 1.8 Mt s hỡnh nh ng dng ca chm lng t CIS ỏnh du hunh quang (a), chiu sỏng (b) v ch to pin mt tri (c) Hỡnh1.9 23 Ph hp th v hunh quang ca cỏc chm lng t CIS ch to dung mụi ODE (hỡnh trờn) v chm lng t CIZS c ch to theo t l Cu:Zn dung mụi ODE 25 10 Hỡnh 1.10 Ph hunh quang ca chm lng t CIS v CIS/ZnS 26 11 Hỡnh 2.1 S thay i ca nng quỏ bóo hũa theo thi gian t 31 12 Hỡnh 2.2 Mt s kt qu mụ phng ca quỏ trỡnh mc mm v phỏt trin ca cỏc nano tinh th Nng ht v quỏ bóo hũa theo thi gian (a) S phỏt trin theo thi gian ca nng ht vi cỏc quỏ bóo hũa khỏc (b), nhit (c), v nng lng t b mt (d) Cỏc hỡnh chốn (b- Footer Page 10 of 89 Header Page 139 of 89 124 TI LIU THAM KHO Ting Vit Trn Th Kim Chi (2010), Hiu ng kớch thc nh hng lờn tớnh cht quang ca CdS, CdSe v CuInS2, Lun ỏn Tin s Khoa hc vt liu Nguyn Quang Liờm (2011), Chm lng t bỏn dn CdSe, CdTe, InP v CuInS2: ch to, tớnh cht quang v ng dng, sỏch chuyờn kho Nh xut bn Khoa hc t nhiờn v cụng ngh, H Ni Nguyn Ngc Long (2007), Vt lý cht rn, Nh xut bn i hc Quc gia H Ni N T M Thy, T T K Chi, N Q Liờm (2011), Tinh th nano CuInS2 ch to dung mụi diesel, Tp húa hc 49, 706-709 N T M Thy, P S Ton, T T K Chi, N Q Liờm (2010), Ch to v nghiờn cu tớnh cht ca tinh th nano CuInS2, Tuyn bỏo cỏo Hi ngh Vt lý cht v Khoa hc vt liu Ton quc ln th NXB Khoa hc T nhiờn v Cụng ngh Tr.258-288 Phm Th Thy (2013), Nghiờn cu ch to v mt s c ch kớch thớch v chuyn hoỏ nng lng vt liu bỏn dn hp cht III-P cu trỳc nanụ, Lun ỏn Tin s Khoa hc vt liu N T M Thy, T T K Chi, N Q Liờm (2013), nh hng ca mt s yu t cụng ngh lờn tớnh cht quang ca cỏc tinh th nano CuInS2 Tp Khoa hc Cụng ngh, ó nhn ng U T D Thỳy, T T K Chi, P S Ton, L Q Phng, P T Thy, N T M Thy, N T Hip, T T T Huyn, N T Loan, N Q Liờm (2013), Vt liu quang in t bỏn dn nanụ: ch to, tớnh cht quang v ng dng,Tp Khoa hc v Cụng ngh, 51, 1-18 Ting Anh A Dijiken, E A Meulenkamp, D Vanmaekelbergh, A J Meijerink (2000), Identification of the transition responsible for the visible Footer Page 139 of 89 Header Page 140 of 89 125 emission in ZnO using quantum size effects, Journal of Luminescence, 90, 123 10 Aby Cheruvathoor Poulose, Srivani Veeranarayanan, Athulya Aravind, Yutaka Nagaoka,Yasuhiko Yoshida, Toru Maekawa, and D Sakthi Kumar (2012), Synthesis of CuAlS2 Nanocrystals and Their Application in Bio-Imaging, Mater Express, Vol 2, No 2, 94 11 Bleuse J., Carayon S., Peter R (2004), "Optical properties of core/multishell CdSe/Zn(S,Se) nanocrystals", Physica E, 21, p 331 12 Booth M., Brown A P., Evans S D., and Critchley K (2012), Determining the Concentration of CuInS2 Quantum Dots from the Size-Dependent Molar Extinction Coefficient, Chem Mater, 24, 2064 13 Castro S L., Bailey S G., Raffaelle R P., Banger K K., Hepp A F (2004), Synthesis and Characterization of Colloidal CuInS2 Nanoparticles from a Molecular SingleSource Precursor, J Phys Chem B, 108, 1242912435 14 Contreras M A., Egaas B., Ramanathan K., Hiltner J., Swartzlander A., Hasoon F., Noufi R (1999), Progress toward 20% efficiency in Cu(In,Ga)Se2 polycrystalline film solar cells, Prog Photovolt Res Appl., 7, 311316 15 Chen B., Zhong H., Zhang W , Tan Z., Li Y., Yu C., Zhai T., Bando Y., Yang S., and Zou Bi (2012), Highly Emissive and Color-Tunable CuInS2-Based Colloidal Stoichiometry Effects Semiconductor and Nanocrystals: Improved Off- Electroluminescence Performance, Adv Funct Mater., 22, 20812088 16 Chen X., Hutchison J L., Dobson P J., Wakefield G (2009 ), "Highly luminescent monodisperse CdSe nanoparticles synthesized in aqueous solution", J Mater Sci., 44, p 285 Footer Page 140 of 89 Header Page 141 of 89 17 126 Chi T T K., Phuong L Q., Liem N Q., Li L., Peter R (2010), "Timeresolved photoluminescence study of CuInS2 nanocrystals", Adv Nat Sci.: Nanosci Nanotech., 1, pp 025007-02501 18 Chi T T K., Thanh D X., and Liem N Q (2007), Luminescence of nano-sized CdS prepared by ball milling, Comm in Phys., 17, 188 19 Chi T T K., Thuy U T D., Liem N Q., Nam M H., Thanh D X (2008), "Temperature-dependent photoluminescence and absorption CdSe quantum dots embbeded in PMMA", J Korean Phys Society, 52, pp 510-513 20 D Pan, X.Wang, Z.Zhou, W.Chen, C Xu, Y F Lu (2009), Synthesis of Quaternary Semiconductor Nanocrystals with Tunable Band Gaps, Chem.Mater., 21, 2489-2493 21 D Valerini, A Creti, M Lomascolo, L Manna, R Cingolani, M Anni (2005), Temperature dependence of the photoluminescence properties of colloidal CdSe/ZnS core/shell quantum dots embedded in a polystyrene matrix, Phys Rev B, 71, 35409 22 Da-Eun Nam, Woo-Seuk Song and Heesun Yang (2011), Facile, airinsensitive solvothermal synthesis of emission-tunable CuInS2/ZnS quantum dots with high quantum yields, J Mater Chem., 21, 1822018226 23 Da-Eun Nam, Woo-Seuk Song, Heesun Yang (2011), Noninjection, one-pot synthesis of Cu-deficient CuInS2/ZnS core/shell quantum dots and their fluorescent properties, Journal of Colloid and Interface Science, 361, 491496 24 Deng D., Chen Y., Cao J., Tian J., Qian Z., Achilefu S., and Gu Y (2012), High-Quality CuInS2/ZnS Quantum Dots for in vitro and in vivo Bioimaging, Chem Mater., 24, 3029 Footer Page 141 of 89 Header Page 142 of 89 25 127 Dmitry Aldakov, Aurelie Lefranỗois and Peter Reiss (2013), Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications, J Mater Chem C, 1, 37563776 26 F Bensebaa, C Durand, A Aouadou, L Scoles, X Du, D Wang, Y Le Page (2010), A new green synthesis method of CuInS2 and CuInSe2 nanoparticles and their integration into thin films, J Nanopart Res., 12, 18971903 27 F Chaffar Akkari, R Brini, M Kanzari and B Rezig (2005), High absorbing CuInS2 thin films growing by oblique angle incidence deposition in presence of thermal gradient, Journal of Materials Scienc, 21, 5751-5755 28 Gao F., Han J., Zhang J., Li Q., Sun X., Zheng J., Bao L., Li X., Liu Z (2011), "The synthesis of newly modified CdTe quantum dots and their application for improvement of latent fingerprint detection", Nanotech., 22, p 075705 29 G Manna, S Jana, R Bose, and N Pradhan (2012), Mn-Doped Multinary CIZS and AIZS Nanocrystals, J Phys Chem Lett., 3, 25282534 30 H S Chen, B Lo, J Y Hwang, G Y Chang, C M Chen, S J Tasi, and S J Wang, J Wang (2004), Colloidal ZnSe, ZnSe/ZnS, and ZnSe/ZnSeS Quantum Dots Synthesized from ZnO, J Phys Chem B 108, 17119 31 H Zhong, S S Lo, T Mirkovic, Y Li, Y Ding, Y Li, G D Scholes (2010), Noninjection Gram-Scale Synthesis of Monodisperse Pyramidal CuInS2 Nanocrystals and Their Size-Dependent Properties, ACS Nano, 10, 1021 32 Haizheng Zhong, Zelong Bai, and Bingsuo Zou (2012), Tuning the Luminescence Properties of Colloidal IIIIVI Semiconductor Footer Page 142 of 89 Header Page 143 of 89 128 Nanocrystals for Optoelectronics and Biotechnology Applications, J Phys Chem Lett., 3, 31673175 33 H Zong, Y Li, M Ye, Z Zhu, Y Zhou, C Yang and Y Li (2007), A facile route to synthesize chalcopyrite CuInSe2 nanocrystals in non coordinating solvent, Nanotechnology, 18, 025602 34 H Nakamura, W Kato, M Uehara, K Nose, T Omata, S Otsuka YaoMatsuo, M Miyazaki, and H Maeda (2006), Tunable Photoluminescence Wavelength of Chalcopyrite CuInS2Based Semiconductor Nanocrystals Synthesized in a Colloidal System, Chem Mater., 18, 33303335 35 H W Hillhouse, M C Beard (2009), Solar cells from colloidal nanocrystals: Fundamentals, materials, devices, and economics, Current Opinion in Colloid & Interface Science, 14, 245259 36 H Wang, Z Shao, B Chen, T Zhang, F Wanga and H Zhong (2012), Transparent, flexible and luminescent composite films by incorporating CuInS2 based quantum dots into a cyanoethyl cellulose matrix, RSC Adv., 2, 26752677 37 Hunter McDaniel, Nobuhiro Fuke, Jeffrey M Pietryga, and Victor I Klimov (2013), Engineered CuInSexS2x Quantum Dots for Sensitized Solar Cells, J Phys Chem Lett., 4, 355361 38 Hyunki Kim, Ji Yeon Han, Dong Seok Kang, Sung Wook Kim, Dong Seon Jang, Minwon Suh, Artavazd Kirakosyan, Duk Young Jeon (2011), Characteristics of CuInS2/ZnS quantumdots and itsapplicationon LED, Journal of Crystal Growth, 326, 9093 39 J S Gardner, E Shurdha, C.Wang, L D Lau, R G Rodriguez, J J Pak (2008), Rapid synthesis and size control of CuInS2 semiconductor nanoparticles using microwave irradiation, J Nanopart Res., 10, 633641 Footer Page 143 of 89 Header Page 144 of 89 40 129 Jaehyun Park and Sang-Wook Kim (2011), CuInS2/ZnS core/shell quantum dots by cation exchange and their blue-shifted photoluminescence, J Mater Chem., 21, 37453750 41 Jang Bo Shim, Chang Gyoun Kim, Dong Ju Jeon, Taek-Mo Chung, KiSeok An, Sun Suk Lee, Jong Sun Lim, Seok Jong Jeong, Bo Keun Park, Young Kuk Lee (2013), Hydrothermal synthesis of CuInSe2 nanoparticles in aceticacid, Journal of Physics and Chemistry of Solids, 74, 867871 42 Jian Feng, Ming Sun, Fan Yanga and Xiurong Yang (2011), A facile approach to synthesize high-quality ZnxCuyInS1.5+x+0.5y nanocrystal emitters, Chem Commun., 47, 64226424 43 Jianping Xiao, Yi Xie,1 Rui Tang, and Yitai Qian (2001), Synthesis and Characterization of Ternary CuInS2 Nanorods via a Hydrothermal Route, Journal of Solid State Chemistry., 161, 179-183 44 Jie Guo, Wen-HuiZhou , MeiLi, Ze-Liang Hou, Jie Jiao, Zheng-JiZhou, Si-Xin Wu (2012), Synthesis of bullet-like wurtzite CuInS2 nanocrystalsunder atmospheric conditions, Journal of Crystal Growth, 359, 7276 45 Jie Zhang, Renguo Xie, and Wensheng Yang (2011), A Simple Route for Highly Luminescent Quaternary Cu-Zn-In-S Nanocrystal Emitters, Chem Mater., 23, 3357336 46 Khare A., Himmetoglu B., Johnson M.,1 Norris D J., Cococcioni M., and Aydil E S (2012), Calculation of the lattice dynamics and Raman spectra of copper Zinc tin chalcogenides and comparison to experiments, J Appl Phys., 111, 083707 47 Katsuhiro Nose, Yuki Soma, Takahisa Omata and Shinya Otsuka-YaoMatsuo (2009), Synthesis of Ternary CuInS2 Nanocrystals; Phase Determination by Complex Ligand Species, Chem Mater., 21, 26072613 Footer Page 144 of 89 Header Page 145 of 89 48 130 Kenneth J Klabunde (2001), Nanoscale materials in chemistry, Wiley interscience 49 Ken-Tye Yong, Indrajit Roy, Rui Hu, Hong Ding, Hongxing Cai, Jing Zhu, Xihe Zhang, Earl J Bergey and Paras N Prasad (2010), Synthesis of ternary CuInS2/ZnS quantum dot bioconjugates and their applications for targeted cancer bioimaging, Integr Biol., 2, 121129 50 Krustok J., Schon J H., Collan H., Yakushev M., Madasson J., and Bucher E (1999), Origin of the deep center photoluminescence in CuGaSe2 and CuInS2 crystals, J Appl Phys., 86, 365369 51 Kuan-ting Chen, Chung-Jie Chiang, Dahtong Ray (2013), Hydrothermal synthesis of chalcopyrite using an environmental friendly chelating agent, Materials Letters, 95, 172174 52 L Qin, D Li, Z Zhang, K Wang, H Ding, R Xie and W Yang (2012), The determination of extinction coefficient of CuInS2, and ZnCuInS3 multinary nanocrystals, Nanoscale , 4, 63606364 53 Li L., Daou T J., Texier I., Chi T T K., Liem N Q., Peter R (2009), "Highly Luminescent CuInS2/ZnS Core/Shell anocrystals: CadmiumFree Quantum Dots for In Vivo Imaging", Chemistry of Materials, 21, pp.2422-2429 54 Li L., Protiốre M., Peter R (2008), "Economic Synthesis of High Quality InP Nanocrystals Using Calcium Phosphide as the Phosphorus Precursor", Chem Mater., 20, p 2621 55 L Li, A Pandey, D J Werder, B P Khanal, J M Pietryga, and V I Klimov (2011), Efficient Synthesis of Highly Luminescent Copper Indium Sulfide-Based Core/Shell Nanocrystals with Surprisingly LongLived Emission, J Am Chem Soc., 133, 1176-1179 Footer Page 145 of 89 Header Page 146 of 89 56 131 Liem N Q., Phuong L Q., Chi T T K., Thuy U T D., Thanh D X (2008), "Polarization of colloidal CdSe quantum dots", J Korean Phys Society, 53, pp.1570-1574 57 Liem N Q., Quang V X., Thanh D X., Lee J I., Kim D (2001), " Temperature dependence of biexciton luminescence in cubic ZnS bulk crystals", Solid State Commu., 117, pp 255259 58 Liu J W., Zhang Y., Ge C W., Jin Y L., Hu S L., Gu N (2009), "Temperature-dependent photoluminescence of highly luminescent water-soluble CdTe quantum dots", Chinese Chem Lett., 20, pp.977980 59 Liu J-H., Fan J-B., Gu Z., Cui J., Xu X-B., Liang Z-W.,Luo S-L, and Zhu M-Q (2008), Green Chemistry for Large-Scale Synthesis of Semiconductor Quantum Dots, Langmuir, 24, 5241-5244 60 Liu Y F., Yu J S (2009), "Selective synthesis of CdTe and high luminescence CdTe/CdS quantum dots: The effect of ligands", J Colloi Inter Sci., 333, pp.690698 61 M Protiốre, P Reiss (2007), Highly Luminescent Cd1-xZnxSe/ZnS Core/Shell Nanocrystals Emitting in the Blue-Green Spectral Range, Small., 3, 399-403 62 M Scocioreanu, M Baibarac, I Baltog, I Pasuk, T.Velula (2012) Photoluminescence and Raman evidence for mechanico-chemical interaction of polyaniline-emeraldine base with ZnS in cubic and hexagonal phase, Journal of Solid State Chemistry, 186, 217223 63 Malik M A., OBrien P., Revaprasadu N (1999), A Novel Route for the Preparation of CuSe and CuInS2 Nanoparticles, Adv Mater, 11,1441-1443 64 Muray C B., Kagan C R., Bawendi M G (2000), "Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystals assemblies", Annu Rev Mater Sci., 30, p 546 Footer Page 146 of 89 Header Page 147 of 89 65 132 M Oda, T Miyaoka, S Yamada, and Toshiro Tani, (2012), "Synthesis, characterization and its photoluminescence properties of group I-III-VI2 CuInS2 nanocrystals, Physics Procedia 29 (2012) 18 24 66 Nam D., Song W and Yang H (2011), Facile, air-insensitive solvothermal synthesis of emission-tunable CuInS2/ZnS quantum dots with high quantum yields, J Mater Chem, 21, 1822018226 67 Nguyen Thi Minh Thuy, Tran Thi Kim Chi, and Nguyen Quang Liem, Low-cost and large-scale synthesis of CuInS2 nanocrystals in diesel, Opt Materials (submitted) 68 Park J., Joo J., Kwon S G., Jang Y., Hyeon T (2007), "Synthesis of monodisperse spherical nanocrystals", Angew Chem Int Ed., 46, p 4630 69 Peter R., Protiốre M., Li L (2009), "Core/Shell Semiconductor Nanocrystals", Small, 5, pp.154-168 70 Protiốre M., Peter R (2007), "Highly Luminescent Cd1-xZnxSe/ZnS Core/Shell Nanocrystals Emitting in the Blue-Green Spectral Range", Small, 3, pp.399-403 71 Qijie Guo, Suk Jun Kim, Mahaprasad Kar, William N Shafarman, Robert W Birkmire, Eric A Stach, Rakesh Agrawal and Hugh W Hillhouse (2007), Development of CuInSe2 Nanocrystal and Nanoring Inks for LowCost Solar Cells, Nanolettters, 8, 29822987 72 Rie X., Rutherford M., and Peng X (2009), Formation of HighQuality I-III-VI Semiconductor Nanocrystals by Tuning Relative Reactivity of Cationic Precursors, J Am Chem Soc., 131, 5691 73 Rogach A L (2008), Semiconductor Nanocrystal quantum Dots: Synthesis, Assembly, Spectroscopy and Applications, Springer, Wien, New York 74 R Zeng, T Zhang, J Liu, S Hu, Q Wan, X Liu, Z Peng, and B Zou (2009), Aqueous synthesis of typeII CdTe/CdSe coreshell quantum Footer Page 147 of 89 Header Page 148 of 89 133 dots for fluorescent probe labeling tumor cells, Nanotechnology, 20, 095102095110 75 Shi A., Wang X., Meng X., Liu X., Li H., Zhao J (2012), Temperature-dependent photoluminescence of CuInS2 quantum dots, Journal of Luminescence, 132, 1819 76 S Shirakata, K Ohkubo, YasuyukiIshii, T Nakada (2009), Effects of CdS buffer layers on photoluminescence properties of Cu(In,Ga)Se2 solar cells, Solar Energy Materials & Solar Cells, 93, 988992 77 Sinnott, Susan B., Andrews, Rodney (2001), "Carbon Nanotubes: Synthesis, Properties, and Applications", Critical Reviews in Solid State and Materials Sciences., 26(3), 145249 78 Siyu Liu, Hao Zhang, Yu Qiao and Xingguang Su (2012), One-pot synthesis of ternary CuInS2 quantum dots with near-infrared fluorescence in aqueous solution, RSC Adv., 2, 819825 79 Siyu Liu, Yanyi Li and Xingguang Su (2012), Determination of copper(II) and cadmium(II) based on ternary CuInS2 quantum dots, Anal Methods, 4, 13651370 80 Song W-S and Yang H (2012), Fabrication of white light-emitting diodes based on solvothermally synthesized copper indium sulfide quantum dots as color converters, Appl Phys Lett., 100, 183104 81 Spiess H W., Haeberlen U., Brandt G., Rauber A., and Schneider J (1974), Nuclear magnetic resonance in I-III-VI2 semiconductors, Phys Status Solidi B, 62, 183 82 S L Castro, S G Bailey, R P Raffaelle, K K Banger, and A F Hepp (2003), Nanocrystalline Chalcopyrite Materials (CuInS2 and CuInSe2) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors, Chem Mater., 15(16), 3142-3147 Footer Page 148 of 89 Header Page 149 of 89 83 134 T Onishi, K Abe, Y Miyoshi, M Iwai and K Wakita (2005), Defect States in CuInS2 Crystals Grown by Traveling Heater Method Jpn J Appl Phys., 44, 722 84 Talapin D V (2002), "Experimental and theoretical studies on the formation of highly luminescent II-VI, III-V and core-shell semiconductor nanocrystals", PhD Thesis, University of Hamburg, Germany 85 Talapin D V., Rogach A L., Haase M and Weller H (2001), Evolution of an Ensemble of Nanoparticles in a Colloidal Solution: Theoretical Study, J Phys Chem B, 105, 12278 86 Talapin D V., Rogach A L., Kornowski A., Haase M., Weller H (2001), "Highly Luminescent Monodisperse CdSe and CdSe/ZnS Nanocrystals Synthesized in a HexadecylamineTrioctylphosphine OxideTrioctylphospine Mixture ", Nano Lett., 1, pp 207-211 87 Talapin D V., Rogach A L., Mekis I., Haubold S., Kornowski A., Haase M., Weller H (2002), "Synthesis and Surface Modification of Amino-Stabilized CdSe, CdTe and InP Nanocrystals", Coll Surf A, 202, pp.145-154 88 Terezia Nyari (2005), Experimental and numerical results in hydrothermal synthesis of CuInS2 compound emiconductor nanocrystals, Journal of Crystal Growth, 275, e2383e2387 89 Toan P S., Thien T D., Liem N Q (2010), "Lager-scale synthesis of CdTe quantum dots in aqueous phase", Communication in Physics, 20, p377 90 T Riedle, (2002), Raman spectroscopy for the Analysis of Thin CuInS2 Films, PhD thesis, Berlin Footer Page 149 of 89 Header Page 150 of 89 91 135 Tzung-Luen Li and Hsisheng Teng (2010), Solution synthesis of highquality CuInS2 quantum dots as sensitizers for TiO2 photoelectrodes, Journal of Materials Chemistry, 20, 36563664 92 Tzung-Luen Li, C Cai, Te-Fu Yeh, H Teng (2013), Capped CuInS2 quantum dots for H2 evolution from water under visible light illumination, Journal of Alloys and Compounds, 550, 326330 93 Tzung-Luen Li, Yuh-Lang Leea and Hsisheng Teng (2012), Highperformance quantum dot-sensitized solar cells based on sensitization with CuInS2 quantum dots/CdS hetero structure, Energy Environ Sci., 5, 53155324 94 Thi Hiep Nguyen, Thu Loan Nguyen, Thi Dieu Thuy Ung and Quang Liem Nguyen (2013), Synthesis and characterization of nano-CuO and CuO/TiO2 photocatalysts, Adv Nat Sci.: Nanosci Nanotechnol., 4, 025002 (6pp) 95 T Pons, E Pic, N Lequeux, E Cassette, L Bezdetnaya, F Guillemin, F Marchal and B Dubertret (2010), Cadmium-Free CuInS2/ZnS Quantum Dots for Sentinel Lymph Node Imaging with Reduced Toxicity, American Chemical Society, 5, 25312538 96 Thuy P T., Chi T T K., Liem N Q (2011), " Temperature-dependent photoluminescence study of InP/ZnS quantum dots.", Advances in Natural Sciences: Nanoscience and nanotechnology, 2, p 025001 97 Thuy P T., Thuy U T D., Chi T T K., Phuong L Q., Liem N Q., Li L., Peter R (2009), "Time-resolved photoluminescence measurement of InP/ZnS quantum dots", J Phys: Conf Series, 187, p 012014 98 Thuy U T D., (2010), Synthesis and characterization of III-V colloidal semiconductor nanocrystals doped with rare-earth ions, Ph.D Thesis Footer Page 150 of 89 Header Page 151 of 89 99 136 Thuy U T D., Huyen T T T., Liem N Q., Peter R (2008), "Low temperature synthesis of InP nanocrystals", Materials Chem Phys., 112, pp 1120-1123 100 Thuy U T D., Liem N Q., Thanh D X., Protiốre M., Peter R (2007), "Optical transitions in polarized CdSe, CdSe/ZnSe, and CdSe/CdS/ZnS quantum dots dispersed in various polar solvents", Appl Phys Lett., 91, p 241908 101 Thuy U T D., Peter R., Liem N Q (2010), "Luminescence properties of In(Zn)P alloy core/ZnS shell quantum dots", Appl Phys Lett, 97, p193104 102 Thuy U T D., Thuy P T., Liem N Q., Li L., Peter R (2010), "Comparative photoluminescence study of close-packed and colloidal InP/ZnS quantum dots", Appl Phys Lett., 96, p 073102 103 Ueng H Y., Hwang H L., (1989), The defect structure of CuInS2 part I: Intrinsic defects, J Phys Chem Solids 50, 1297 104 Ung T D Thuy, Tran T K Chi , Pham T Nga, Nguyen D Nghia , D D Khang and Nguyen Q Liem, (2012), CdTe and CdSe quantum dots: synthesis, characterizations and applications in agriculture, Adv Nat Sci: Nanosci Nanotechnol, 3, 043001 105 W H Koschel and M Bettini (1975), Zone-centered phonons in AIBIIIS2 chalcopyrites, Phys stat sol (b), 72, 729737 106 Wang Y., Chen H., Ye C., Hu Y (2008), "Synthesis and characterization of CdTe quantum dots embedded gelatin nanoparticles via a two-step desolvation method", Mat Lett., 62, pp.33823384 107 Wei-Dong Xiang, Hai-Long Yang, Xiao-Juan Liang, Jia-Song Zhong, Jing Wang, Le Luo and Cui-Ping Xie (2013), Direct synthesis of highly luminescent CuZnInS quaternary nanocrystals with tunable, J Mater Chem C, 1, 20142020 Footer Page 151 of 89 Header Page 152 of 89 137 108 Weisheng Guo, Na Chen, Chunhong Dong, Yu Tu,b Jin Chang and Bingbo Zhang (2013), One-pot synthesis of hydrophilic ZnCuInS/ZnS quantum dots for in vivo imaging, RSC Adv., 3, 94709475 109 W Guo, N chen, Y Tu, C Dong, B Zhang, C Hu, and J Chang (2013), Synthesis of Zn-Cu-In-S/ZnS Core/Shell Quantum Dots with Inhibited Blue-Shift Photoluminescence and Applications for Tumor Targeted Bioimaging, Theranostics, Vol 3, Issue 2, 99-108 110 Wei-Wei Xiong, G Yang, X Wu, and Jun-Jie Zhu (2013), Aqueous Synthesis of Color-Tunable CuInS2/ZnS Nanocrystals for the Detection of Human Interleukin 6, ACS Appl Mater Interfaces, 5(6), 8210 111 W Yue, F Wu, C Liu, Z Qiu, QiCui, H Zhang, F Gao, W Shen, Q Qiao, M Wang (2013), Incorporating CuInS2 quantum dots into polymer/oxide-nanoarraysystem for efficient hybrid sola rcells, Solar Energy Materials & Solar Cells, 114, 4353 112 Wenjin Zhang and Xinhua Zhong (2011), Facile Synthesis of ZnS_CuInS2-Alloyed Nanocrystals for a Color-Tunable Fluorchrome and Photocatalyst, Inorg Chem., 50, 40654072 113 Woggon U (1997), Optical Properties of Semiconductor Quantum dot, Springer Tracts in Modern Physics 114 X Yuan, J Zhao, P Jing, W Zhang, H Li, L Zhang, X Zhong, and Y Masumoto (2012), Size- and Composition-Dependent Energy Transfer from Charge Transporting Materials to ZnCuInS Quantum Dots, J Phys Chem C, 116, 1197311979 115 Xue Gao, Xingcen Liu, Zihan Lin, Siyu Liu and Xingguang Su (2012), CuInS2 quantum dots as a near-infrared fluorescent probe for detecting thrombin in human serum, Analyst., 137, 56205624 Footer Page 152 of 89 Header Page 153 of 89 138 116 Yacobi B G., Brada Y., Lachish U., Hirsch C (1975.), "Phonongenerated microfields and temperature dependence of the absorption edge in II-VI compounds", Phys Rev B, 11, p 2990 117 Yakushev M V., Martin R W., Mudryi A.V and Ivaniu Kovich A V (2008), Excited states of a free exciton in CuInS2, Appl Phys Lett, 92, 111908 118 Yanyan Chen, Shenjie Li, Lijian Huang, and Daocheng Pan (2013), Green and Facile Synthesis of Water-Soluble CuInS/ZnS Core/Shell Quantum Dots, Inorg Chem., 52, 78197821 119 Yuhan Lin, Fang Zhang and Daocheng Pan (2012), A facile route to (ZnS)x(CuInS2)1-x hierarchical microspheres with excellent watersplitting ability, J Mater Chem., 22, 2261922623 120 Zhang Y., Zhang H., Ma M., Guo X., Wang H (2009), "The influence of ligands on the preparation and optical properties of water-soluble CdTe quantum dots", Appl Surf Sci., 255, pp 47474753 121 Tariq J ALWAN and Mushtak A JABBAR (2010), Structure and optical properties of CuAlS2 thin films prepared via chemical bath deposition, 34, 107 116 122 W Liu, Y Zhang, W Zhai, Y Wang, T Zhang, P Gu, H Chu, H Zhang, T Cui, Y Wang, J Zhao, W W Yu (2013) TemperatureDependent Photoluminescence of ZnCuInS/ZnSe/ZnS Quantum Dots, The Journal of Physical Chemistry, xxx, xxx-xxx Footer Page 153 of 89 ... DỤC VÀ ÐÀO TẠO VIỆN HÀN LÂM KH & CN VIỆT NAM VIỆN KHOA HỌC VẬT LIỆU NGUYỄN THỊ MINH THỦY NGHIÊN CỨU CHẾ TẠO VÀ TÍNH CHẤT QUANG CỦA CHẤM LƯỢNG TỬ BÁN DẪN HỢP CHẤT BA NGUYÊN TỐ I-III-VI2 (CuInS2). .. luận án ' 'Nghiên cứu chế tạo tính chất quang chấm lượng tử bán dẫn hợp chất ba nguyên tố I-III-VI2 (CuInS2)" Footer Page 17 of 89 Header Page 18 of 89 Mục đích luận án Nghiên cứu chế tạo thành... trúc chấm lượng tử hợp chất CuIn(Zn)S2 80 Header Page of 89 3.3 Chấm lượng tử hợp chất CuIn(Al)S2 82 3.3.1 Chế tạo chấm lượng tử hợp chất CuIn(Al)S2 82 3.3.2 Cấu trúc chấm lượng tử hợp chất CuIn(Al)S2