温度梯度法制备CeF_3光学镀膜材料的工艺研究
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摘要
以自制的CeF_3粉体为原料,在真空碳管炉中采用温度梯度法制备了CeF_3晶体。通过X射线衍射(XRD)、扫描式电子显微镜(SEM)、能谱分析(EDS)等分析方法对不同影响因素下的产物进行表征,CeF_3晶体进行镀膜实验,并对所得膜层进行光学性能测试。结果表明:采用钨坩埚,在1×10-2Pa真空度下1500℃保温1 h,以100℃·h-1的温度梯度降温,可制备得结晶性能良好的CeF_3晶体。添加NH4HF2作为脱氧剂可以使产物中氧含量从0. 54%(质量分数)降低到0. 1%。采用两种氧含量的CeF_3晶体分别进行镀膜实验,氧含量较低的晶体,其镀膜速率波动曲线较稳定,在±0. 05 nm·s-1之间波动,说明氧含量的降低可显著改善材料的蒸发特性;镀膜残余由发黑、发白、黑白过度三部分组成,其发黑部分氧含量最高为7. 92%。CeF_3膜层性能测试表明,在波长为550 nm处,折射率为1. 6,吸收系数为3×10-4。
CeF_3 crystal was prepared by temperature gradient method in vacuum carbon tube furnace with self-made CeF_3 powder as raw material. The products under different influence factors were characterized by X-ray diffraction( XRD),scanning electron microscope( SEM),energy dispersive spectrometer( EDS). CeF_3 crystals were subjected to coating experiments,and the optical properties of the films were tested. The results showed that CeF_3 crystal with good crystallinity could be prepared using tungsten crucible,keeping it at 1500 ℃ for 1 h and the vacuum was 1 × 10-2 Pa,the temperature gradient was 100 ℃·h-1. The addition of NH4 HF2 as a deoxidizer reduced the oxygen content of the product from 0. 54% to 0. 1 %( mass fraction). The CeF_3 crystals with two kinds of oxygen content were used for the coating experiment. The crystal with low oxygen content was stable and fluctuated between ± 0. 05 nm·s-1,which indicated that the decrease of oxygen content could improve the evaporation characteristics of the material; the coating residue was composed of black part,white part,black and white part,and the oxygen content of the black part was 7. 92%. The CeF_3 film performance test showed that the refractive index was 1. 6 and the absorption coefficient was 3 × 10-4 at a wavelength of 550 nm.
CeF_3 crystal was prepared by temperature gradient method in vacuum carbon tube furnace with self-made CeF_3 powder as raw material. The products under different influence factors were characterized by X-ray diffraction( XRD),scanning electron microscope( SEM),energy dispersive spectrometer( EDS). CeF_3 crystals were subjected to coating experiments,and the optical properties of the films were tested. The results showed that CeF_3 crystal with good crystallinity could be prepared using tungsten crucible,keeping it at 1500 ℃ for 1 h and the vacuum was 1 × 10-2 Pa,the temperature gradient was 100 ℃·h-1. The addition of NH4 HF2 as a deoxidizer reduced the oxygen content of the product from 0. 54% to 0. 1 %( mass fraction). The CeF_3 crystals with two kinds of oxygen content were used for the coating experiment. The crystal with low oxygen content was stable and fluctuated between ± 0. 05 nm·s-1,which indicated that the decrease of oxygen content could improve the evaporation characteristics of the material; the coating residue was composed of black part,white part,black and white part,and the oxygen content of the black part was 7. 92%. The CeF_3 film performance test showed that the refractive index was 1. 6 and the absorption coefficient was 3 × 10-4 at a wavelength of 550 nm.
引文
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[2] Yu H S,Colfen H,Armin F. High quality Ce O2nanocrystals stabilized by a double hydrophilic block copolymer[J]. Colloids Surf. A,2004,243(123):49.
[3] Li X Z,Chen Y,Chen Z G,Chen J G,Ni C Y. Preparation of Ce O2nanoparticles and their chemical mechanical polishing as abrasives[J]. Journal of Tribology,2007,27(1):125.(李霞章,陈杨,陈志刚,陈建清,倪超英.纳米Ce O2颗粒的制备及其化学机械抛光性能研究[J].摩擦学学报,2007,27(1):125.)
[4] Hasegawa Y,Imanaka N,Adachi G. Cerium ion conducting solid electrolyte[J]. J. Solid State Chem.,2003,171(122):387.
[5] Kaspar J,Fornasiero P,Graziani M. Use of Ce O2based oxides in the three-way catalysis[J]. Catal Today,1999,50(2):285.
[6] Qu X F,Xu Y Q. Nano material application in the lubricant of automobile engine[J]. Vehicle Engine,2003,(2):31.(曲晓峰,徐元强.纳米材料在汽车发动机机油中的应用[J].车用发动机,2003,(2):31.)
[7] Su W T,Li B,Liu D Q,Li D Q,Zhang F S. The fitting of optical constants of infrared coating materials and application in broad band antireflection coatings[J]. Acta Photonica Sinicas,2008,37(3):490.(苏伟涛,李斌,刘定权,李大琪,张凤山.红外光学薄膜材料光学常量计算和在宽带增透膜中的应用[J].光子学报,2008,37(3):490.)
[8] Zhao C L,Hu Y S,Chen K,Xu H B,Shao L L,Ye H Q.Research progress in silicon-based(oxy)nitride phosphors for phosphor-converted white LED[J]. Chinese Journal of Rare Metals,2017,41(12)1374.(赵春雷,胡运生,陈凯,徐会兵,邵冷冷,叶红齐.白光LED用硅基氮(氧)化物荧光粉的研究进展[J].稀有金属,2017,41(12):1374.)
[9] Hu M C,Ye W Y,Zhou D Z,Guo C. Study on time properties of newly type inorganic scintillator cerium fluoride(Ce F3)[J]. Nuclear Electronics&Detection Technology,2003,23(5):411.(胡孟春,叶文英,周殿忠,郭存.新型无机闪烁体Ce F3的时间特性研究[J].核电子学与探测技术,2003,23(5):411.)
[10] Su W T,Li B,Liu D Q,Zhang F S. The relation between crystal structure and infrared optical properties of Er F3film[J]. Acta Physica Sinica,2007,56(5):2541.(苏伟涛,李斌,刘定权,张凤山.氟化铒薄膜晶体结构与红外光学性能的关系[J].物理学报,2007,56(5):2541.)
[11] Xue C R,Yi K,Shao J D. Preparation of 157 nm fluoride optical thin films[J]. Acta Photonica Sinica,2010,39(11):1961.(薛春荣,易葵,邵建达. 157 nm氟化物光学薄膜制备[J].光子学报,2010,39(11):1961.)
[12] Z Y Q,S E W,Li W J,Wang B G,Hu X F. Research and development of the theories of crystal growth[J]. Journal of Inorganic Materials,1999,(3):1.
[13] Li L C,Xue K M. Review and prospect of the equipment for growing crystals[J]. Journal of Synthetic Crystals,2002,(3):329.
[14] Lage M M,Moreira R L,Matinaga F M,et al. Raman and infrared reflectivity determination of phonon modes and crystal structure of Czochralski grown Na Ln F4(Ln=La,Ce,Pr,Sm,Eu,and Gd)single crystals[J]. Chemistry of Materials,2005,17(17):4523.
[15] Yu Y G,Yao S H,Xu M,Wang X P,Zhang H J,Wang J Y. Automatic diameter controlling for crystal growth with CZ method[J]. Journal of Synthetic Crystals,2008,(1):16.
[16] Laudise R A. The Growth of Single Crystals[M]. New Jersey,Prentice-Hall. 1970. 168.
[17] Steven Duly,Jon-Paul R Wells,Hugh G Gallagher,Thomas P J Han. Bridgman growth and laser excitation of Li YF4:Sm3+[J]. Journal of Crystal Growth,1999,203:405.
[18] LüJ J,Wang J B,Ouyang J L,Xue Q J. The thermal stability of Ce F3and the effect of decomposed product on friction wear properties and its mechanism[J]. Tribology,1996,(4):330.(吕晋军,王静波,欧阳锦林,薛群基.三氟化铈的高温热稳定性及其分解产物对摩擦磨损性能的影响和作用机理[J].摩擦学学报,1996,(4):330.)