Nghiên cứu các tính chất của vật liệu sắt điện không chứa chì nền Bi0,5(NaK)0,5TiO3(BNKT) pha tạp li dạng khối và BNKT20 dạng màng

BỘ GIÁO DỤC VÀ ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI NGƠ ĐỨC QN NGHIÊN CỨU CÁC TÍNH CHẤT CỦA VẬT LIỆU SẮT ĐIỆN KHƠNG CHỨA CHÌ NỀN Bi0,5(NaK)0,5TiO3 (BNKT) PHA TẠP Li DẠNG KHỐI VÀ BNKT20 DẠNG MÀNG LUẬN ÁN TIẾN SĨ KHOA HỌC VẬT LIỆU Hà Nội – 2016 BỘ GIÁO DỤC VÀ ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI NGÔ ĐỨC QUÂN NGHIÊN CỨU CÁC TÍNH CHẤT CỦA VẬT LIỆU SẮT ĐIỆN KHƠNG CHỨA CHÌ NỀN Bi0,5(NaK)0,5TiO3 (BNKT) PHA TẠP Li DẠNG KHỐI VÀ BNKT20 DẠNG MÀNG Chuyên ngành: Vật liệu điện tử Mã số: 62440123 LUẬN ÁN TIẾN SĨ KHOA HỌC VẬT LIỆU NGƯỜI HƯỚNG DẪN KHOA HỌC: PGS.TS VŨ NGỌC HÙNG TS ĐẶNG ĐỨC DŨNG Hà Nội – 2016 I LỜI CAM ĐOAN Tôi xin cam đoan cơng trình nghiên cứu riêng tơi hướng dẫn PGS TS Vũ Ngọc Hùng TS Đặng Đức Dũng Các số liệu kết luận án hoàn toàn trung thực chưa cơng bố cơng trình khoa học khác Thay mặt Tập thể hướng dẫn Tác giả PGS TS Vũ Ngọc Hùng Ngô Đức Quân II LỜI CÁM ƠN Trước hết tơi xin bày tỏ lòng kính trọng biết ơn sâu sắc đến PGS TS Vũ Ngọc Hùng TS Đặng Đức Dũng, người thầy tận tình hướng dẫn, giúp đỡ tạo điều kiện thuận lợi cho tơi q trình thực luận án Những lúc gặp khó khăn cản trở công việc sống, thầy ln bên quan tâm, động viên, khích lệ tơi kịp thời Là nhà khoa học mẫu mực, thầy truyền cảm hứng, truyền lửa cho giúp tơi vượt qua thử thách, khó khăn để học tập, để nghiên cứu khoa học vươn tới đỉnh cao trí thức Tơi xin chân thành cảm ơn Viện ITIMS, Viện Đào tạo Sau đại học Viện Vật lý kỹ thuật, trường ĐH Bách Khoa Hà Nội tạo điều kiện thời gian, vật chất tinh thần giúp tơi hồn thành luận án Tơi xin chân thành cảm ơn TS Nguyễn Đức Minh, TS Chu Mạnh Hoàng, TS Vũ Thu Hiền, ThS Phạm Ngọc Thảo anh chị bạn phòng thí nghiệm MEMS, Viện ITIMS, trường ĐH Bách Khoa Hà Nội động viên chia sẻ kinh nghiệm nghiên cứu khoa học có thảo luận đóng góp bổ ích giúp tơi hồn thiện luận án Tơi xin gửi lời cảm ơn sâu sắc tới GS Ill Won Kim GS Sunglae Cho, Khoa Vật lý, trường ĐH Ulsan, Hàn Quốc hỗ trợ kinh phí tạo điều kiện thuận lợi cho thực phép đo đạc luận án Tôi xin cảm ơn TS Dương Anh Tuấn PGS TS Aman Ullah tận tình giúp đỡ hướng dẫn sử dụng hệ đo Tôi xin gửi lời cảm ơn tới anh em, bạn bè, đồng nghiệp người thân bên, động viên khích lệ tơi thời gian qua Tôi xin cảm ơn anh chị đồng nghiệp môn Vật lý đại cương, Viện Vật lý kỹ thuật, trường ĐH Bách Khoa Hà Nội quan tâm, hỗ trợ tơi cơng việc để tơi có điều kiện hoàn thành luận án III Cuối tơi xin bày tỏ lòng biết ơn vơ hạn tới người thân u gia đình tơi Sự động viên hy sinh thầm lặng bố mẹ, vợ em tình cảm vơ giá, động lực tinh thần lớn lao khích lệ tơi vượt qua khó khăn trở ngại học tập sống để đạt kết cuối Hà Nội, ngày 12 tháng 04 năm 2016 Tác giả Ngô Đức Quân IV DANH MỤC CHỮ VIẾT TẮT VÀ CÁC KÝ HIỆU Các ký hiệu STT Ký hiệu Thuật ngữ Tiếng Anh A The area of electrodes Diện tích điện cực (m2) C The Curie constant Hằng số Curie Cg The grain capacitance Điện dung nội hạt (F) Cgb The grain capacitance Điện dung biên hạt (F) cijkl The elastic stiffness tensor Di The total surface charge Mật độ điện tích bề mặt tồn density phần (Cm-2) dijk The piezoelectric coefficient Hệ số áp điện (CN-1) EC The coercive field Trường điện kháng (V/m) Eg The band gap Độ rộng vùng cấm (eV) 10 Ɛg The grain conduction Năng lượng hoạt hóa dẫn nội activation energy hạt (eV) 11 Ɛgb The grain boundary Năng lượng hoạt hóa dẫn biên conduction activation energy hạt (eV) 12 Ei The electric field vector 13 JFN The Fowler-Nordheim Mật độ dòng xuyên ngầm current density Fowler-Nordheim (A/cm2) 14 JPF 15 JSCLC 16 JSch 17 kij The electromechanical Các thành phần hệ số liên coupling coefficient kết điện 18 kp The boundary Thuật ngữ Tiếng Việt Các thành phần ten-sơ suất Young (Nm-2) Điện trường ngồi (Vm-1) The Poole-Frenkel current Mật độ dòng Poole-Frenkel (A/cm2) density The space charge current Mật độ dòng điện tích khơng density gian (A/cm2) The Schottky current density planar Mật độ dòng Schottky (A/cm2) coupling Hệ số liên kết bề mặt V coefficient The thickness coupling Hệ số liên kết theo chiều dày 19 kt 20 M* The electric mudulus Modul điện 21 Pi The polarization Độ phân cực (C.m−2) 22 pi The pyroelectric coefficient Hệ số hỏa điện (Cm-2K-1) 23 Pr The remanent polarization Độ phân cực dư (C/m2) 24 Ps The spontaneous polarization Độ phân cực tự phát (C/m2) 25 Rg The grain resistance Điện trở nội hạt (Ω) 26 Rgb The grain resistance Điện trở biên hạt (Ω) 27 sijkl The elastic compliance 28 T 29 T0 30 TB The Burn temperature Nhiệt độ Burn (°C, K) sắt điện re-la-xo 31 TC The Curie point Điểm Curie (°C, K) 32 Td The temperature Nhiệt đảo pha (°C, K) 33 Xij The stress Ứng suất (Nm-2) 34 xij The strain Độ biến dạng (%) 35 Z' The real part of impedance Phần thực trở kháng phức 36 Z'' The imaginary of impedance Phần ảo trở kháng phức 37 Z* The complex impedance Trở kháng phức (Ω) 38 α The absorption Độ hấp thụ 39 δij The Kronecker’s symbol Ký hiệu Kronecker 40 ε* The complex constant Hằng số điện môi phức 41 ε0 The dielectric permittiverty Hằng số điện môi tuyệt đối of a vacuum (Fm-1) 42 εij The dielectric permittivity Hằng số điện môi vật liệu 43 κij The relative permittivity Hằng số điện môi tương đối coefficient boundary đàn hồi (m2N-1) Nhiệt độ (°C, K) The temperature The Các thành phần ten-sơ suất Curie–Weiss temperature depolarization dielectric dielectric Nhiệt Curie–Weiss (°C, K) VI 44 τg 45 τgb 46 χij The dielectric susceptibility 47 бg The grain conductivity 48 бgb The grain relaxation time The grain boundary relaxation time The grain Thời gian hồi phục nội hạt (s) Thời gian hồi phục biên hạt (s) Các thành phần ten-sơ độ cảm điện môi (Fm-1) Độ dẫn nội hạt (S/m) boundary conductivity Độ dẫn biên hạt (S/m) Các chữ viết tắt STT Ký hiệu Thuật ngữ Tiếng Anh Thuật ngữ Tiếng Việt AFE Antiferroelectrics Phản sắt điện AFM Atomic-Force Microscopy Kính hiển vi lực nguyên tử BFO BiFeO3 BKT Bi0,5K0,5TiO3 BNKT BNKT20 Bi0,5(Na0,80K0,20)0,5TiO3 BNKTS Bi0,5(Na,K)0,5Ti0,95Sn0,05O3 BNKTZ Bi0,5(Na,K)0,5Ti0,97Zr0,03O3 BNT Bi0,5Na0,5TiO3 10 BTO BaTiO3 11 CVD Chemical Vapor Deposition Lắng đọng pha hóa học 12 EFIS Electric-Field-Induced Strain Hệ số biến dạng gây điện trường 13 FE Ferroelectrics Sắt điện 14 FE-SEM 15 FN 16 MEMS 17 18 Bi0,5(Na,K)0,5TiO3 Field Emission Scanning Hiển vi điện tử quét phát xạ Electron Microscope trường Fowler-Nordheim Hiệu ứng Fowler-Nordheim MicroElectroMechanical Systems Hệ vi điện tử MPB Morphotropic Boundary Biên pha hình thái học PF Poole-Frenkel Phase Hiệu ứng Poole-Frenkel VII A Commercial Lead 19 PIC151 20 PIC255 21 PLD Pulsed Laser Deposition 22 PLZT (Pb,La)(Zr,Ti)O3 23 PMN Pb(Mg1/3Nb2/3)O3 24 PT 25 PZT PbZriO3 - PbTiO3 26 RQ Root Mean Roughness 27 SBT SrBi2Ta2O9 28 SCLC Space Charge Current 29 XRD X-Ray Diffraction Zirconate Titanate Ceramic Gốm PZT thương mại A Commercial Lead Gốm PZT thương mại Zirconate Titanate Ceramic Lắng đọng xung Laser PbTiO3 Square Độ nhám tồn phương trung bình Limited Dòng điện tích khơng gian Nhiễu xạ tia X VIII DANH MỤC HÌNH VẼ STT Tên hình vẽ Trang Hình 1.1 Một số kiểu cấu trúc vật liệu sắt điện: (a) Cấu trúc tinh thể pe-rov-skit ABO3 pha lập phương, (b) Cấu trúc pe-rov-skit LiNbO3 LiTaO3, (c) Cấu trúc kiểu lớp bi- 11 smut SrBi2Ta2O9 (SBT), (d) Cấu trúc kiểu đồng – vonfram (A1)2(A2)4(C)4(B1)2(B2)8O30 [25] Hình 1.2 Sự biến đổi cấu trúc BaTiO3 theo nhiệt độ [3] Hình 1.3 Sự chuyển pha từ pha lập phương thuận điện sang pha tứ giác sắt điện theo nhiệt độ vật liệu sắt điện Đường cong hệ số điện môi liệu đo gốm BaTiO3 Mũi tên hướng phân cực tự phát Ô đơn vị thể hình vng pha lập phương hình chữ nhật pha tứ giác [36] 12 13 Hình 1.4 Cấu trúc perovskite ABO3 PbTiO3 với cấu trúc lập phương pha thuận điện cấu trúc tứ giác pha sắt điện Hình 1.5 (a) Domain sắt điện 180o (b) 90o vùng vách domain chất sắt điện perovksite tứ giác Sơ đồ thay đổi độ phân cực qua vách domain 180o thể hình (a) Sự méo mạng tứ giác phóng đại hình (b) Hình 1.6 Sự hình thành vách domain sắt điện 90o 180o chất sắt điện perovskite tứ giác PbTiO3 Sự biến dạng tinh thể miền vách domain hình thành vách 90o 15 16 17 phóng đại Các ký hiệu giải 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Zvirgzds A., Kapostins P P and Zvirgzde J V (1982) X-ray study of phase transitions in ferroelectric Na0.5Bi0.5TiO3 Ferroelectrics 40, pp 75-77 ... trung vào vai trò tạp chất đến tính chất áp điện BNKT Kết mở phương hướng để nâng cao tính chất vật li u sắt điện khơng chì 1.1 Tính chất sắt điện vật li u 1.1.1 Cấu trúc vật li u Cho dù vật li u. .. GIÁO DỤC VÀ ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI NGƠ ĐỨC QN NGHIÊN CỨU CÁC TÍNH CHẤT CỦA VẬT LI U SẮT ĐIỆN KHƠNG CHỨA CHÌ NỀN Bi0,5(NaK)0,5TiO3 (BNKT) PHA TẠP Li DẠNG KHỐI VÀ BNKT20 DẠNG MÀNG... đồng pha tạp Li, Sn BNKT đồng pha tạp Li, Zr phương pháp phản ứng pha rắn Nghiên cứu ảnh hưởng nồng độ pha tạp lên cấu trúc, tính chất sắt điện, tính chất áp điện tính chất quang vật li u Trên