DAI HOC QUOC GIA HA NOI NGHIEN CtJU CHE TAO CHUYEN MACH NHIET QUANG VA UNG DUNG (Bao cao tong hgp De tai Nghien ciiu khoa hoc dac biet cap Dai hoc Qu6c gia Ha Noi) OAI HOC QUOC GIA HA NOI TI^UNG TAM THONG TIN THU VIEN PT/5r>^ Ma so: QG-04.01 Chu nhiem de tai: PGS-TS NGUYfiN NANG DINH Ha Noi 2005 MUC lUC « « ' ^^ I PHAN MODAU LI Cac chu viet tat 1.2 Danh sach nhihig ngudi tham gia thuc hien 1.3 Danh muc cac hinh 1.4 Tom tdt nhung ket qua chinh II NOI DUNG CHINH Dat va'n de Tong quan cac va'n de nghien cun Dia diem, thoi gian va phuong phap nghien cihi Noi dung va ket qua nghien cun 4.1 Noi dung cac bao cao chuyen de 4.2 Cong nghe che tao mlu va phuong phap nghien ciiu 4.3 Ket qua nghien cun 4.3.1 Che tao mSu 4.3.2 Nghien cun tinh chat Thao luan va kien nghi 5.1 Thao luan 5.2 Kien nghi III TAI L E U THAM KHAO IV PHULUC V PHIEU DANG K? KET QUA NGHIEN CLfU KH-CN L PHAN Md DAU LI Cac chur viet tdt KHVL: Khoa hoc vat lieu DHCN: Dai hoc Cong nghe BDKL: Ban dan - Kim loai NDP: Nhiet d6 phong NDCP: Nhiet chuyen pha SEM: Scanning Electron Microscope (Hien vi dien tu quet) XRD: X-ray diffraction (Nhieu xa tia X) 1.2 Danh sach nhOmg nguoi tham gia thuc hien STT Ho ten Co quan cong tac Trucmg DHCN, DHQGHN PGS-TS Nguyen Nang Dinh TS Tran Thi Tam - Th.S.Vu Ngoc Cham - TS.Nguyen Phuong Hoai Nam - PGS-TS Nguyln Thi Bao Ngoc - HVCH Le Ha Chi - TS Pham Duy Long KS D6 Xuan Mai - CN- Dang Van Thanh - 10 KSC Dang Quoc Trung - 11 KSC Tran Anh Vu - 12 KS Le Huu Minh - 13 NCS Th.S.Le Dinh Trong Vien KHVL, Vien KHCN VN DHSP Ha Noi II, Xuan Hoa 1.3 Danh muc cac hinh Hinh So d6 he chan khong co chum tia dien tir Sling dien tu, Chen va vat lieu goc, De va ga de co be'p d6t, Van dieu chinh d5ng 6xy, Tu dieu khien Hmh Anh SEM be mat mang mong oxyt vanadi hoc bay bangky thuat chu tia dien tu Hinh Gian XRD tren mang VO2 tai NDP (A), dot nong 80°C (B) va Sc de ngu6i vl NDP (C), Hmh Pho tan xa Raman cua mang mong VO2 tai nhiet 25 **C-NDP (1), t 90 '^C (2) va tra lai NDP (3) Hinh Anh SEM mat cat vuong goc cua mang mong VOj Hinh Dien trd suat phu thuoc vao nhiet cua mang mong VO2 Hinh Pho truyen qua cua mang mong VO2 tai nhiet 27 '^C (< x^) va 90' Hmh Anh SEM chyp be mat cua mang VO2 truac (phan tren) va sau ket tinh (phan duoi) Hmh Pho truyen qua cua mang VO2 nano tai hai vung nhiet thap hi NDCP (30°C) va cao hon NDCP (80°C) Hmh 10 Pho truyen qua ciia mang VO2 nano tai hai vung nhiet thap b NDCP (30°C) va cao hon NDCP (80°C) Hmh 11 So cau tao cam bien nhiet quang 1- Dau sgi quang co phu lop mang mong VO2 2- Bg phat, thu laser va so sanh tin hieu nhiet-quang 3- Vi tinh va hien thi so sanh 1.4 Tom tdt nhOmg ket qua chinh Ten de tai: Nghien curu che tao chuyen mach nhiet quang va ung dung Ma so: QG-04.01 Nhufng ket qua chinh a, Ket qua ve khoa hpc (nhirng dong gop cua de tai, cac cong trinh khoa hoc cong bo) Xay dung phuong phap cong nghe che' tao mang VO2 micro va nano co tinh chSit cam bien nhiet quang Cac ke't qua chinh dugc tong ke't a cong trinh va bao cao khoa hoc dudi day: Nguyln Nang Dinh, Linh kien quang dien tu tren ca sa mang mong VO2 che tao bang chum tia dien tii Tap chi Khoa hoc DHQGHN, KHTN&CN, T.XXI, so 2AP (2005)tr.8-15 Nguyln Nang Dinh, Le Dinh Trgng, Ifng dung phd tdng trd de nghien cicu tinh chat ddn ion cua mang mong chat ran Tap chi khoa hgc va cong nghe, Vien KH&CN Viet Nam , nhan dang 12/2005 N.N.Dinh, T.T.Tam, V.X.Huong, D.H.Thanh, Electrical and Optical properties of nano-structured VO2 thin films prepared by e-beam deposition, Gui dang Coom.in Physics, nhan dang 12/2005, Nguyen Nang Dinh, Do Phuong Anh, Le Dinh Trong, Electrochromic properties of vanadium oxide films made by high voltage spraying Advances in Nat.Sci., nhan dang 12/2005 Nguyln Nang Dinh, Tran Thi Tam, Nghien cihi che tao cam bien nhiet quang tren casdmdng mong VO2 cau trite nano, B/c tai Hoi nghi Vat ly toan quoc lan thii 6, Ha Noi, 23-25/11/2005 b, Ket qudphiic vu thitc te(cAc san pham cong nghe, kha nang ung dung thuc it) Che tao thu cam bien nhiet quang, co hieu ung cam bien tot, Co the ap dung vao thuc te giam sat nhiet moi truong chat long, doc lai K^iU UlZ-t/i^-Nl^V^iT^ , c Ket qua dao tao (s6' lugng sinh vien, hgc vien cao hgc, NCS lam viec de tai) Le Binh Trgng NCS nam thii hai; da co ket qua tdt ve che' tao mSu bang chum tia dien tir, khao sat tinh chsft nhiet sac va cam bien nhiet quang Trdn Quang Trung NCS nam cu6'i; da hoan Ban thao luan an TS, se bao ve luan an nam 2006 Le Hd Chi Hgc vien Cao hgc KION; se bao ve luan van thang 12 nam 2005 d Kit qua ndng cao tiem luc khoa hgc (nang cao trinh can bg va tang cucmg tran^ thiet bi cho don vi) Nang cao trinh NCKH cho tap the khoa hgc, giang vien nhom Dl tai Trong mot s6' can bg tiir trinh d6 cut nhan thac sy, tijr thac sy tien sy Gop phan nang ca'p mot sd he thuc nghiem phuc vu dac tinh cha't dien e Tinh hinh sii diing kinh phi Da quyet toan dSy dia va dung theo quy dinh cua Phong Ke toan-Tai vu Trucmg Dai hgc Cong nghe, DHQGHN CHU NHIEM DE TAI XAC NHAN CUA DON VI HIEU TRUONG ^^.t^rp>e^^S^ PGS-TS Nguyln Nang Dinh f T XAC NHAN CO QUAN CHU QUAN L Titlle of the project: Investigation of preparation of thermo-optical switching and application Project code: QG-04.01 Main results a Scientific results (contributions and pubhcations) Developing technological method for preparation of micro- and nanostructured vanadium dioxide films with thermo-optical switching properies The results have been reported in published scientific works, as follows: N N Dinh, Opto-electronic devices based on VO2 thin films made by electronbeam-deposition, J Sci.VNUH, Nat.Sci.&Tech., V.XXI, No.2AR (2005) pp.8-15 N N Dinh, L D Trong, Application of impedance technique for investigation oi ionic conducting properties of tliin solid films, J Sci & Tech VAST, to be pubhsbed in Dec 2005 N.N.Dinh, T.T.Tam, V.X.Huong, D.H.Thanh, Electrical and Optical properties oj nano-structured VO2 thin films prepared by e-beam deposition, J Coom ir Physics, to be published in Dec 2005 Nguyen Nang Dinh, Do Phuong Anh, Le Dinh Trong, Electrochromic properties of vanadium oxide films made by high voltage spraying Advances in Nat.Sci., tc be pubhshed in Dec 2005 N N Dinh, T T Tam, Investigation of preparation of thermo-optical sensors based on nanostructured VO2 thin films, Proc the 6-th Nat.Conf.on Physics Hanoi 23-25/11/2005 b Application results (produces, application potentials) Preparation of prototype thermo-optical svv^itching devices used for monitoring temperature change in oil or/and gaseous toxic storages c Education results (number of students of BS, MSc and doctors working in tht subject) Le Dinh Trong, Mr Ph.D student in the second academic year; having good results in electron-beam technique for samples preparation and characterisation of theirs properties Tran Quang Trung, Ph.D student in the last year; fulfilled the dissertation Mr being defended in next year (2006) Le Ha Chi, Mrs MSc student -¥1^ Cao hgc KION; se bao ve luan van thang 12 nam 2005 d Results in the improvement of scientific power (scientific staff-members and equipments) Improvement of science and technology experiences of the team, some of them have been got higher degree in science, e.g from BS to MSc., from MSc to Ph.D degrees Partial contribution in up-grading some characterization set-ups e Financial expenditures Efficient use of the provided finacial sum of 60 milion VND and this sum has been completely cleared up Director of the Project Assoc.Prof Nguyen Nang Dinh n NOI DUNG CHINH Datv^nde Vat ueu nhiet quang hay ggi la nhiet sdc (thermochromic) dugc nhieu tap the khoa hgc tren the gidi chii trgng nghien cun la vat lieu co nhieu tinh cha't dac biet ly thu va kha nang ung dung vao thuc tiln rat tilm tang, Trong so vat lieu nhiet quang thi mang mong VO2 la vat lieu thich hgp nhat de thie't ke' che' tao b6 dong ngat he vi chuyen mach th6ng minh Oxyt vanadi khong hgp thu'e co tinh cha't nhay khi, nhit la ddi vdi loai doc hai hay dl chay nhu hcfi Khi mang mong 6xyt vanadi tiep xiic vdi loai thi dien tro bl mat thay doi dang ke Vi vay, mang mong 6xyt vanadi co trien vgng ung dung linh vuc sensor de bao d6c, bao chay gop ph^n gin giu va bao ve moi trucmg Mot tinh cha't quan trgng khac cua VO2 the hien a ch6 nhiet d6 ciia mang dat den diem chuyen pha ban din kim loai thi ca tinh chat dien va quang ciia chung deu bie'n d6i mot each dot nggt va mang tinh thuan nghich Do vay, viec nghien cun cong nghe che' tao chuyen mach nhiet quang khong nhung gop phSn nang cao trinh d6 khoa hgc cong nghe vl quang dien tu va quang tu cho can bg khoa hgc, giang vien ma md kha nang ung dung vao thuc tiln che' tao cam bien nhiet quang su dung de phat hien nguong nhiet d6 cua moi trucmg gay chay no, doc hai ciia cha't long, xang ddu hay cha't Tong quan cac van de nghien cihi - Nhu cSu bao chay tai cac kho tang gidi hay cac tram xang dau cang tro nen cap bach Hien viec bao chay dugc thuc hien thong qua cac cam bien nhiet va bao khoi chi thuc hien dugc tai cac cong trinh cong cong, nha a, kho kho De bao nguong nhiet nguy hiem tec xang dau hay a nhung khu vuc kho tang gidi bi mat dat each xa tram quan sat thi cac cam bie'n hien dang su dung la khong thich hgp Do la phan Idn cam bien nhiet dien diu phai dung den dien truong (dien the') hay dong dien, phai nhung chim xang dau se gay nguy hiem hoac khoang each tCr noi dat cam bie'n den may qua Idn khie'n chinh xac giam nhanh - De khac phuc cac nhugc diem tren co the su dung loai senso nhiet-quang, senso lam viec tren nguyen ly nhiet tang den mot nguong nhat dinh thi chiet suat cua vat lieu senso thay doi, dan den truyen qua/phan xa thay doi Qua viec giam sat truyen qua, phan xa cua vat lieu co the phat hien-chinh xac su thay d6i cua nhiet moi truong (chat hoac chat long) Loai cam bien co uu diim: • Su dung cap quang truyin tin hieu cho nen co the dat dau cam bien vao chat long hay tai cac dia diim each xa tram theo doi; • -i „ La m6t loai cam bien nhiet - quang cho nen d^ tri hoat dong ciia senso khong cdn co dong dien - Dl tai nghien ciiu mang tinh cong nghe cao, tap trung giai quyet cac va'n dl vl sii dung ky thuat bdc bay chiam tia dien tit di che' tao mang mong VO2 co tinh chit nhiet sac, CO kha nang cam bie'n nhiet quang; nghien cun cac tinh cha't chuyin mach nhiet quang ciia mSu mang mong VO2 ctfu tnic micro, nano va kha nang iing dung ciia cam bi^n nhiet quang Che tao mang mong VO2 nhiet sac tren co s6 oxyt vanadi co thi tien hanh bang nhilu phuong phap khac nhau, nhien ky thuat chan kh6ng dung chum tia dien tii (bdc bay chiim tia dien tii) vSn la mdt sd phuong phap mang lai ket qua tdt va hieu qua Cac budc cong nghe phuong phap chiim tia dien tii va anh hudng ciia che' d6 cong nghe len tinh chat vat ly ciia mang mong VO2, dac biet la tinh chat nhietquang la cac va'n de chinh nghien cun cong nghe che' tao mlu Trong do, cac tham sd cong nghe nhu tdc d6 bdc bay, nhiet d6 de, dieu kien xir ly nhiet, cac loai de' khac nhu thuy tinh phang, cap quang, dugc chii trgng nghien cun Trong phan nghien ciiu tinh cha't, di tai tap trung vao dac trung tinh cha't chuyen mach nhiet dien va nhiet quang ciia mang VO2 che' tao bang chiim tia dien tii Co che' va tinh cha't nhiet sdc, kha nang cam bie'n nhiet quang cua vat lieu mang mong Dia diem, thcri gian va phuong phap nghien curu Cac nghien ciiu cong nghe dugc tien hanh tai PTN lien ke't giiia Trucmg Dai hgc Cong nghe (DHQGHN) va Vien Khoa hgc Vat lieu (Vien KHCNVN) Nghien ciiu va dac trung tfnh cha't dugc tien hanh tai Khoa Vat ly ky thuat va Cong nghe nano, Truong DHCN Sii dung cac trang thiet bi Khoa va ciia Trung tam KHVL, Trucmg DHKHTN (DHQGHN) , Vien KHVL, Vien KHCNVN dl phan tich ca'u triic vat lieu, dac cac thong sd va dac trung cac tinh chat ciia mang mong VO2 Thoi gian nghien cun dugc bat dau tii 5/2004 va ket thiic vao thang 12/2005 Noi dung va ket qua nghien curu 4.L Noi dung cac bao cao chuyen de Chuyen de ''Cong nghe chitm tia dien tu vd che tao mang mong nhiet quang " Trinh bay tdng quan cac phuong phap che tao mang mong nhiet s k tren co so oxyt vanadi, co ky thuat chan khong dung chiim tia dien tir (phuong phap 10 •Mftt^^i} »/» J VI iiurui ocience, /// (2005), ?? ELECTROCHROMIC PROPERTIES OF VANADIUM OXIDE FILMS MADE BY HIGH VOLTAGE SPRAYING NGUYEN NANG DINH, DO PHUONG ANH College of Technology, Hanoi Vietnam National University, Hanoi DO HONG THANH Tuyen-Quang College of Pedagogy Trung Mon, Yen Son, Tuyen Quang Abstract, Vanadium oxide thin films were prepared by spraying in a high Dc-voltage of 12 kV Solutions of VCI3 in alcohol served as the initial spraying source Crystalline and molecular structures have been checked, respectively by XRD and Raman scattering spectra In situ optical measurements combining with cyclic voltammety have proved a good reversible electrochromic effect of the fdms in UCIOA + PC solution and under polarized potential of ± I.5V The electrochromic efficiency vs wavelength was determined from OMA spectra and insertion charge In visible and NIR ranges it was found to be as high as 22 cm^/C and 28.5 cm^/C, respectively From the study one can suggest an application of the technological method to produce vanadium oxide films used for both the electrochromic display devices and gaseous sensors Introduction Electrochromic effect of tungsten oxide films has been discovered in 1969 by S.K Deb and found potential applications in solar energy management, all-solid state display devices, etc [1,2] Later [3], this effect has also been investigated for vanadium oxide films like VO2 and VOx However, the fact that the price of the devices is still rather high is the main reason why these materials are not used widely as liquid crystal display Recently, conducting polymers, which can be served as solid electrolyte for the electrochromic device (ECD), are intensively studied with the aim to lower the price in comparison with solid inorganic electrolyte The other way to deal with this problem is to develop simpler and cheaper techniques to deposit the films It has been known that both tungsten and vanadium oxide films can be prepared by using numerous expensive methods, such as vacuum evaporation, electron beam deposition, Dc- and Rf-sputtering, plasma-enhanced CVD Techniques like anodic deposition, electroless and/or electrochemical deposition have also been used Although these techniques meet requirement on the reduced price, it is much more difficult to control the technological conditions to get the films with a quality as high as the first group of the methods does Spray hydrolysis is a simple and promising method that can be used for preparation of different kinds of thin films This technique becomes more efficient when the spraying process is carried-out under high Dcvoltage Electrochromism of WO3 films is believed to be directly related to the double injection/extraction of electron and ions under the applied electric field and can be expressed by following equation [4-5]: WO3 (colorless) + x(M^ + e")