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一种用于光波导的Ge-Se-Zn硫系薄膜材料及其制备方法 【EN】A kind of Ge-Se-Zn Chalcogenide films material and preparation method thereof for optical waveguide

申请(专利)号:CN201610250638.X国省代码:浙江 33
申请(专利权)人:【中文】宁波大学【EN】Ningbo University
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摘要:
【中文】本发明公开了一种用于光波导的Zn‑Se‑Ge硫系薄膜材料及其制备方法,特点其化学结构式为ZnxSeyGez,其中28<x<40,30<y<45,15<z<40,x+y+z=100;其制备方法如下:将ZnSe合金靶材安装在磁控射频溅射靶中,将Ge单质靶材安装在磁控直流靶中,将磁控溅射镀膜系统的溅射腔室进行抽真空至室内真空度达到2.5×10‑4Pa,然后通入为50ml/min的高纯氩气直至起辉气压0.25Pa,然后控制Ge靶的溅射功率为0‑11W,ZnSe合金靶的溅射功率固定为70W,于室温下溅射镀膜即可,优点是稳定性高,粗糙度低,透过率较高,短波截止边较短,薄膜组分偏差小,结构稳定。 【EN】Paragraph:The Zn-Se-Ge Chalcogenide films material and preparation method thereof that the invention discloses a kind of for optical waveguide, its chemical structural formula of feature are ZnxSeyGez, wherein 28 < x < 40,30 < y < 45,15 < z < 40, x+y+z=100;Preparation method is as follows: ZnSe alloy target material being mounted in magnetron RF sputtering system target, Ge simple substance target is mounted in magnetic control direct current target, carries out the sputtering chamber of magnetron sputtering coating system to be evacuated to house vacuum degree and reaches 2.5 × 10‑4Pa, the high-purity argon gas for 50ml/min is then passed to until build-up of luminance air pressure 0.25Pa, then the sputtering power for controlling Ge target is 0-11W, and the sputtering power of ZnSe alloys target is fixed as 70W, at room temperature sputter coating, advantage is stability height, roughness is low, and transmitance is higher, and short wavelength cutoff side is shorter, film composition deviation is small, stable structure.Image:201610250638.GIF

主权项:
【中文】1.一种用于光波导的Ge-Se-Zn硫系薄膜材料,其特征在于:该材料为Zn-Se-Ge的化合物,其化学结构式为ZnSeGe,其中33.4≤x≤37.8,35.1≤y≤43.3,18.9≤z≤31.5,x+y+z=100。 【EN】1. a kind of Ge-Se-Zn Chalcogenide films material for optical waveguide, it is characterised in that: the material is the chemical combination of Zn-Se-Ge Object, chemical structural formula ZnSeGe, wherein 33.4≤x≤37.8,35.1≤y≤43.3,18.9≤z≤31.5, x+y+z =100。


说明书

【中文】

一种用于光波导的Ge-Se-Zn硫系薄膜材料及其制备方法

技术领域

本发明涉及光电子学领域,尤其是涉及一种用于光波导的Ge-Se-Zn硫系薄膜及其制备方法。

背景技术

硫系玻璃由于其结构的灵活性(硫族元素低配位且价带中最高处孤对电子的存在),在近带隙光照下会表现出许多光致变化现象,从而引起电子及原子结构、物相、物理化学性质等变化。例如,沉积态的硫系薄膜在激光诱导下,其短波吸收截止边有可能发生红移,向长波方向移动(即光致暗化),也有可能发生蓝移,向短波方向移动(即光致漂白),并会造成折射率变化。光照还有可能造成体积(比如光致膨胀现象)、粘度(光致流动)、机械性能(光致机械效应)、物相(比如光致非晶化以及光致析晶)等变化。目前,研究Ge-Se非晶硫系薄膜的光诱导效应是科研热点,该效应可以用于光学存储材料、制备布拉格光栅、光波导等方面。专利申请公开号CN103572218A “一种光致稳定非线性硫系薄膜及制备方法”,研究表明Ge-As-S-Se薄膜光致折射率变化极小,器件光学性能稳定,薄膜的抗激光损伤阈值较高,有利于器件在非线性光学领域的应用。但是As是有毒元素且采用热蒸发镀膜方法易对环境与实验人员造成污染及危害。因此研究新型不含As的硫系薄膜材料并探索光诱导结构变化对器件光学特性的稳定有重要的价值。ZnSe晶体具有非常宽的光谱覆盖范围(0.6~22um),常用来制造用于高能量红外激光器的各种光学元件(窗片、反射镜、透镜),但其高昂的价格以及差的热稳定性阻碍了其应用范围的拓宽。ZnSe硫系薄膜具有优异的光学性能,并且由于其独特的对光响应极其敏感的结构特点,易于发生光致变化,在光学存储以及其他光学领域具有很好的应用前景,但是制备的沉积态薄膜易于析晶,稳定性较差。

发明内容

本发明所要解决的技术问题是提供一种稳定性高,粗糙度低,透过率较高,短波截止边较短,薄膜组分偏差小的用于光波导的Ge-Se-Zn硫系薄膜材料及其制备方法。

本发明解决上述技术问题所采用的技术方案为:一种用于光波导的Ge-Se-Zn硫系薄膜材料,该材料为Zn-Se-Ge的化合物,其化学结构式为ZnxSeyGez,其中28<x<40,30<y<45,15<z<40,x+y+z=100。

其化学结构式为ZnxSeyGez,优选x=33.4,y=35.1,z=31.5。

采用ZnSe合金靶和Ge单质靶双靶磁控共溅射。

上述用于光波导的Ge-Se-Zn硫系薄膜材料的制备方法,利用磁控溅射镀膜系统,采用双靶共溅射方法制备获得,具体包括下述步骤:在磁控溅射镀膜系统中,采用石英片或氧化硅片为衬底,将ZnSe合金靶材安装在磁控射频溅射靶中,将Ge单质靶材安装在磁控直流靶中,将磁控溅射镀膜系统的溅射腔室进行抽真空直至室内真空度达到2.5×10-4Pa,然后向溅射腔室内通入体积流量为50ml/min的高纯氩气直至溅射腔室内气压达到溅射所需起辉气压0.25Pa,然后控制Ge靶的溅射功率为0-11W, ZnSe合金靶的溅射功率固定为70W,于室温下溅射镀膜,控制溅射厚度为0.5-1.2µm,即得到沉积态的Ge-Se-Zn薄膜材料,其化学结构式为ZnxSeyGez,其中28<x<40,30<y<45,15<z<40,x+y+z=100。

其化学结构式为ZnxSeyGez,优选x=33.4,y=35.1,z=31.5。

与现有技术相比,本发明的优点在于:本发明一种用于光波导的Ge-Se-Zn硫系薄膜材料,其化学结构式为ZnxSeyGez, ,其中028<x<40,30<y<45,15<z<40,x+y+z=100。

提出在ZnSe薄膜中引入金属Ge,研究三元Ge-Se-Zn薄膜结构在热处理、光照前后硫系薄膜内部结构的变化,结果表明制备的Zn-Se-Ge薄膜材料相较于ZnSe薄膜,表现出良好的非晶态特性,稳定性高,粗糙度降低,透过率较高,短波截止边较短,光漂白和光暗化变化显著,薄膜组分偏差小,结构稳定。较佳的优选组分可为Zn33.4Se35.1Ge31.5,具有较高的稳定性,粗糙度低,薄膜组分偏差较小。上述薄膜材料作为光波导传输材料,可以大大提高光波导的稳定性,薄膜均匀平整性好且低的粗糙度有利于降低光传输损耗,通过磁控溅射方法获得的不同批次薄膜重复性得到控制,薄膜组分一致,结构可控。解决了常用硫系薄膜在使用过程中由于光致变化导致光学性能不稳定问题,这对于制备高稳定光学材料具有重要指导意义。

附图说明

图1为ZnSe薄膜X射线衍射图谱;

图2 为Zn-Se-Ge薄膜的X射线衍射图谱;

图3为ZnSe,Zn-Se-Ge薄膜的透过率变化;

图4为ZnSe薄膜的实时光致透过率变化;

图5为70ZnSe-5Ge薄膜的实时光致透过率变化;

图6为1µm厚70ZnSe-11Ge薄膜的实时光致透过率变化;

图7为0.65µm厚70ZnSe-11Ge薄膜的X射线衍射图;

图8为0.62µm厚70ZnSe-11Ge薄膜的X射线衍射图;

图9为0.65µm厚70ZnSe-11Ge薄膜的拉曼光谱;

图10为0.62µm厚70ZnSe-11Ge薄膜的拉曼光谱。

具体实施方式

以下结合附图实施例对本发明作进一步详细描述。

一、具体实施例

实施例1

本发明一种用于光波导的Ge-Se-Zn硫系薄膜材料,其化学结构式为ZnxSeyGez,其中28<x<40,30<y<45,15<z<40,x+y+z=100,其具体制备过程如下:

在磁控溅射镀膜系统中,采用石英片或氧化硅片为衬底,将ZnSe合金靶材安装在磁控射频溅射靶中,将Ge靶材安装在磁控直流溅射靶中,将磁控溅射镀膜系统的溅射腔室进行抽真空直至室内真空度达到2.4×10-4Pa,然后向溅射腔室内通入体积流量为50ml/min的高纯氩气直至溅射腔室内气压达到溅射所需起辉气压0.25Pa,然后控制ZnSe合金靶的溅射功率为70W,Ge单质靶的溅射功率为5W,于室温下溅射镀膜,溅射厚度为1µm后,即得到沉积态的ZnxSeyGez薄膜,其中x=37.8,y=43.3,z=18.9,即Zn37.8Se43.3Ge18.9

将制备的薄膜进行X射线衍射(XRD)和原子力显微镜(AFM)性能测试,测试结果如图2和表1所示,从图2和表1中可以看出实施例1制备的薄膜的性能指标如下;沉积态薄膜是非晶态,粗糙度是2.316nm,透过率为60%,短波截止边为750nm。

实施例2

与实施例1基本相同,其区别在于,溅射过程中,控制合金ZnSe靶的溅射功率为70W,Ge单质靶的溅射功率为8W,薄膜厚度控制在1µm,得到的ZnxSeyGez薄膜,其中x=35.1,y=39,z=25.9,即Zn35.1Se39Ge25.9

将制备的薄膜进行XRD和AFM性能测试,测试结果如图2和表1所示,从图2和表1中可以看出实施例2制备的薄膜的性能指标如下;沉积态薄膜是非晶态,粗糙度是1.745,透过率为50%,短波截止边为850nm。

实施例3

与实施例1基本相同,其区别在于,溅射过程中,控制合金ZnSe靶的溅射功率为70W,Ge单质靶的溅射功率为11W,薄膜厚度控制在1µm,得到的ZnxSeyGez薄膜,其中x=33.4,y=35.1,z=31.5,即Zn33.4Sb35.1Te31.5

将制备的薄膜进行XRD和AFM性能测试,测试结果如图2和表1所示,从图2和表1中可以看出实施例3制备的薄膜性能指标如下:沉积态薄膜是非晶态,粗糙度是1.214nm,透过率是40%,短波截止边是1000nm。

实施例4

与实施例3相同,溅射过程中,控制合金ZnSe靶的溅射功率为70W,Ge单质靶的溅射功率为11W,其区别在于降低溅射的速度,薄膜厚度控制在0.65µm,得到的ZnxSeyGez薄膜,其中x=32.5,y=34.8,z=32.7,即Zn32.5Sb34.8Te32.7

实施例5

与实施例3相同,溅射过程中,控制合金ZnSe靶的溅射功率为70W,Ge单质靶的溅射功率为11W,其区别在于降低溅射的速度,薄膜厚度控制在0.62µm,得到的ZnxSeyGez薄膜,其中x=30.1,y=35.2,z=34.7,即Zn30.1Sb35.2Te34.7

将制备的不同厚度的70ZnSe-11Ge薄膜进行XRD和Raman性能测试,测试结果如图7,8,9,10,从图中可以看出实施例4-5制备的薄膜性能指标如下:不同厚度的沉积态薄膜均是非晶态,薄膜重复性得到控制,薄膜组分一致,结构可控。

二、对比试验及结果分析

1、对照试验

与实施例1基本相同,其区别在于ZnSe合金靶的溅射功率为70W,Ge单质靶的溅射功率为0W,于室温下溅射镀膜,溅射厚度约为1µm后,即得到沉积态的ZnSe薄膜。将制备的薄膜进行XRD和AFM性能测试,测试结果如图1和表1所示,可以看出对照实施例1制备的薄膜性能指标如下:沉积态ZnSe薄膜已经析晶,ZnSe粗糙度(RMS)是3.558nm,此外,光学透过谱揭示透过率为80%,其短波截止边为500nm。上述对照实验与上述实施例1、实施例2和实施例3的靶材溅射功率,Zn、Se、Ge含量及相关参数如表1所示。

表1 不同条件下制备的1µm厚Zn-Se-Ge薄膜材料及相关参数

2、结果分析

将实施例1、实施例2、和实施例3中制备的薄膜进行X射线衍射测试,测试结果如图1和图2所示。

图1测试了沉积态ZnSe薄膜的X射线衍射图。室温下制备的ZnSe薄膜呈现一个析晶峰,表明沉积态已经部分结晶。引入Ge后如图2所示,沉积态的Zn-Se-Ge的薄膜均表现出典型的非晶态晕图,没有晶体颗粒析出,表明制备的Zn-Se-Ge薄膜是非晶态性质。根据原子力显微镜测试薄膜表面粗糙度如表1显示,ZnSe的粗糙度是3.558nm,随着Ge的引入,且溅射功率不断增加,70ZnSe-5Ge,70ZnSe-8Ge和70ZnSe-11Ge薄膜的粗糙度减小为2.316nm,1.745nm,1.214nm。说明制备的Zn-Se-Ge薄膜表面均匀平整。

图3给出了Zn-Se-Ge中ZnSe,70ZnSe-5Ge 和70ZnSe-11Ge沉积态薄膜透过光谱。从图中可以看出,沉积态的ZnSe薄膜具有较高的的透过率为80%,短波截止边为500nm。随着Ge的引入,其短波截止边出现向长波方向移动,从500nm移到1000nm。透过率为40-60%之间。

图4给出了ZnSe薄膜的实时光致变化,结果发现其透过率随波长未出现光致漂白或光致暗化现象。

图5给出了实施例1制备的70ZnSe-5Ge薄膜的实时光致变化现象,结果发现其透过率随着波长增加出现了连续的光致暗化直至透过率为负数。

图6给出了实施例3制备的70ZnSe-11Ge薄膜的实时光致变化现象,结果发现其透过率随着波长增加先出现了光致漂白后暗化再漂白,表现出了较强的光敏特性。

图7和图8分别给出了0.65µm和0.62µm厚的70ZnSe-11Ge薄膜的X射线衍射图,证实不同厚度制备的薄膜均是非晶态特性。

图9和图10分别给出了0.65µm和0.62µm厚的70ZnSe-11Ge薄膜的拉曼光谱图,证实了不同厚度制备的组分均匀薄膜具有相同的结构。

综上所述,本发明制备的Zn-Se-Ge薄膜材料的稳定性高,粗糙度低,透过率较高,短波截止边较短,薄膜组分偏差小,结构稳定;较佳的,优选溅射功率70ZnSe-11Ge双靶制备的薄膜即Zn33.4Se35.1Ge31.5,具有较高的稳定性,粗糙度低,薄膜组分偏差较小,光致变化明显。

当然,上述说明并非对本发明的限制,本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内做出的变化、改型、添加或替换,也应属于本发明保护范围。

【EN】

A kind of Ge-Se-Zn Chalcogenide films material and preparation method thereof for optical waveguide

Technical field

The present invention relates to opto-electronics, more particularly, to a kind of Ge-Se-Zn Chalcogenide films for optical waveguide and its

Preparation method.

Background technique

Chalcogenide glass is since (highest point lone pair electrons are deposited in the low coordination of chalcogen and valence band for the flexibility of its structure

), many photic variation phenomenons can be shown, under nearly band gap illumination so as to cause electronics and atomic structure, object phase, physico

Learn the variation such as property.For example, the Chalcogenide films of deposited, under induced with laser, short-wave absorption cut-off side is likely to occur red

It moves, it is mobile (i.e. photodarkening) to long wave direction, it is also possible to blue shift occurs, it is mobile (i.e. photobleaching) to shortwave direction, and

It will cause variations in refractive index.Illumination is it is also possible to cause volume (such as photoexpansion phenomenon), viscosity (photic flowing), mechanicalness

The variation such as energy (photic mechanical effect), object phase (such as photic decrystallized and photic crystallization).Currently, research Ge-Se amorphous sulphur

The lightinduced adsorption for being film is scientific research hot spot, which can be used for Optical storage media, prepares Bragg grating, optical waveguide

Etc..Patent application publication number CN103572218A " one kind is photic to stablize non-linear Chalcogenide films and preparation method ", research

Show that Ge-As-S-Se film photon-induced refractive index changes very little, device optical performance is stablized, the threshold for resisting laser damage of film compared with

Height is conducive to device in the application of non-linear optical field.But As is toxic element and uses thermal evaporation film plating process easily right

Environment is polluted and is endangered with experimenter.Therefore it studies the novel Chalcogenide films material without As and explores photo-induction guide structure

Variation has important value to the stabilization of device optical characteristic.ZnSe crystal has very wide spectral coverage (0.6~22

Um), the various optical elements (window, reflecting mirror, lens) that manufacture is used for high-energy infrared laser are commonly used to, but its is high

The thermal stability of price and difference hinders widening for its application range.ZnSe Chalcogenide films have excellent optical property, and

And due to its unique design feature extremely sensitive to photoresponse, it is prone to photic variation, optical storage and other

Optical field has a good application prospect, but the As-deposited film prepared is easy to crystallization, and stability is poor.

Summary of the invention

It is high that technical problem to be solved by the invention is to provide a kind of stability, and roughness is low, and transmitance is higher, and shortwave is cut

Only side is shorter, the small Ge-Se-Zn Chalcogenide films material and preparation method thereof for optical waveguide of film composition deviation.

The technical scheme of the invention to solve the technical problem is: a kind of Ge-Se-Zn sulphur system for optical waveguide

Thin-film material, the material are the compound of Zn-Se-Ge, chemical structural formula ZnxSeyGez, wherein 28 < x < 40,30 < y < 45,

15 < z < 40, x+y+z=100.

Its chemical structural formula is ZnxSeyGez, preferably x=33.4, y=35.1, z=31.5.

Using ZnSe alloys target and the double target magnetic control co-sputterings of Ge simple substance target.

The preparation method of the above-mentioned Ge-Se-Zn Chalcogenide films material for optical waveguide, using magnetron sputtering coating system,

Prepared using double target co-sputtering method, specifically include the following steps: in magnetron sputtering coating system, using quartz plate or

Oxidized silicon chip is substrate, and ZnSe alloy target material is mounted in magnetron RF sputtering system target, and it is straight that Ge simple substance target is mounted on magnetic control

It flows in target, the sputtering chamber of magnetron sputtering coating system vacuumize until house vacuum degree reaches 2.5 × 10-4Pa, so

The high-purity argon gas that volume flow is 50ml/min is passed through in backward sputtering chamber until sputtering chamber room pressure reaches needed for sputtering

Build-up of luminance air pressure 0.25Pa, the sputtering power for then controlling Ge target is 0-11W, and the sputtering power of ZnSe alloys target is fixed as 70W,

Sputter coating at room temperature, control sputtering are arrived the Ge-Se-Zn thin-film material of deposited with a thickness of 0.5-1.2 μm, are changed

Structural formula is ZnxSeyGez, wherein 28 < x < 40,30 < y < 45,15 < z < 40, x+y+z=100.

Its chemical structural formula is ZnxSeyGez, preferably x=33.4, y=35.1, z=31.5.

Compared with the prior art, the advantages of the present invention are as follows: a kind of Ge-Se-Zn sulphur system for optical waveguide of the invention is thin

Membrane material, chemical structural formula ZnxSeyGez, wherein 028 < x < 40,30 < y < 45,15 < z < 40, x+y+z=100.

It proposes to introduce metal Ge in ZnSe film, research ternary Ge-Se-Zn membrane structure is before and after heat treatment, illumination

The variation of Chalcogenide films internal structure, the results showed that the Zn-Se-Ge thin-film material of preparation is shown good compared to ZnSe film

Good amorphous character, stability is high, and roughness reduces, and transmitance is higher, and short wavelength cutoff side is shorter, and photobleaching and brightnessization become

Change significantly, film composition deviation is small, stable structure.Preferable preferred ingredient can be Zn33.4Se35.1Ge31.5, with higher steady

Qualitative, roughness is low, and film composition deviation is smaller.Above-mentioned thin-film material can greatly improve light as optical waveguide transmission material

The stability of waveguide, the good and low roughness of film uniform ground advantageously reduces optical transmission loss, by magnetron sputtering side

The different batches film repeatability that method obtains is controlled, and film composition is consistent, structure-controllable.It solves common Chalcogenide films to exist

Since photic variation leads to optical property instability problem in use process, this is for preparing high stable optical material with important

Directive significance.

Detailed description of the invention

Fig. 1 is ZnSe film X ray diffracting spectrum;

Fig. 2 is the X ray diffracting spectrum of Zn-Se-Ge film;

Fig. 3 is ZnSe, the transmitance variation of Zn-Se-Ge film;

Fig. 4 is the real-time photic transmitance variation of ZnSe film;

Fig. 5 is the real-time photic transmitance variation of 70ZnSe-5Ge film;

Fig. 6 is the real-time photic transmitance variation of 1 μ m-thick 70ZnSe-11Ge film;

Fig. 7 is the X-ray diffractogram of 0.65 μ m-thick 70ZnSe-11Ge film;

Fig. 8 is the X-ray diffractogram of 0.62 μ m-thick 70ZnSe-11Ge film;

Fig. 9 is the Raman spectrum of 0.65 μ m-thick 70ZnSe-11Ge film;

Figure 10 is the Raman spectrum of 0.62 μ m-thick 70ZnSe-11Ge film.

Specific embodiment

The present invention will be described in further detail below with reference to the embodiments of the drawings.

One, specific embodiment

Embodiment 1

A kind of Ge-Se-Zn Chalcogenide films material for optical waveguide of the present invention, chemical structural formula ZnxSeyGez,

In 28 < x < 40,30 < y < 45,15 < z < 40, x+y+z=100, specific preparation process is as follows:

It in magnetron sputtering coating system, uses quartz plate or oxidized silicon chip for substrate, ZnSe alloy target material is mounted on

In magnetron RF sputtering system target, Ge target is mounted in magnetic control d.c. sputtering target, by the sputtering chamber of magnetron sputtering coating system

Vacuumize until house vacuum degree reaches 2.4 × 10-4Pa, it is 50ml/min that volume flow is then passed through into sputtering chamber

High-purity argon gas until sputtering chamber room pressure reach sputtering needed for build-up of luminance air pressure 0.25Pa, then control splashing for ZnSe alloys target

Penetrating power is 70W, and the sputtering power of Ge simple substance target is 5W, at room temperature sputter coating, sputtering with a thickness of after 1 μm to get to heavy

The Zn of product statexSeyGezFilm, wherein x=37.8, y=43.3, z=18.9, i.e. Zn37.8Se43.3Ge18.9

The film of preparation is subjected to X-ray diffraction (XRD) and atomic force microscope (AFM) performance test, test result is such as

Shown in Fig. 2 and table 1, it can be seen that the performance indicator of film prepared by embodiment 1 is as follows from Fig. 2 and table 1;As-deposited film is

Amorphous state, roughness are 2.316nm, and transmitance 60%, short wavelength cutoff side is 750nm.

Embodiment 2

Substantially the same manner as Example 1, difference is, in sputtering process, the sputtering power of control alloy ZnSe target is

The sputtering power of 70W, Ge simple substance target is 8W, and plastics thickness control is at 1 μm, obtained ZnxSeyGezFilm, wherein x=35.1, y=

39, z=25.9, i.e. Zn35.1Se39Ge25.9

The film of preparation is subjected to XRD and AFM performance test, test result is as shown in Figure 2 and Table 1, from Fig. 2 and table 1

It can be seen that the performance indicator of film prepared by embodiment 2 is as follows;As-deposited film is amorphous state, and roughness is 1.745, is penetrated

Rate is 50%, and short wavelength cutoff side is 850nm.

Embodiment 3

Substantially the same manner as Example 1, difference is, in sputtering process, the sputtering power of control alloy ZnSe target is

The sputtering power of 70W, Ge simple substance target is 11W, and plastics thickness control is at 1 μm, obtained ZnxSeyGezFilm, wherein x=33.4, y

=35.1, z=31.5, i.e. Zn33.4Sb35.1Te31.5

The film of preparation is subjected to XRD and AFM performance test, test result is as shown in Figure 2 and Table 1, from Fig. 2 and table 1

It can be seen that film performance index prepared by embodiment 3 is as follows: As-deposited film is amorphous state, and roughness is 1.214nm, is penetrated

Rate is 40%, and short wavelength cutoff side is 1000nm.

Embodiment 4

Same as Example 3, in sputtering process, the sputtering power of control alloy ZnSe target is 70W, the sputtering of Ge simple substance target

Power is 11W, and difference is to reduce the speed of sputtering, and plastics thickness control is at 0.65 μm, obtained ZnxSeyGezFilm,

Middle x=32.5, y=34.8, z=32.7, i.e. Zn32.5Sb34.8Te32.7

Embodiment 5

Same as Example 3, in sputtering process, the sputtering power of control alloy ZnSe target is 70W, the sputtering of Ge simple substance target

Power is 11W, and difference is to reduce the speed of sputtering, and plastics thickness control is at 0.62 μm, obtained ZnxSeyGezFilm,

Middle x=30.1, y=35.2, z=34.7, i.e. Zn30.1Sb35.2Te34.7

The 70ZnSe-11Ge film of the different-thickness of preparation is subjected to XRD and Raman performance test, test result is as schemed

7,8,9,10, as can be seen from the figure the film performance index of embodiment 4-5 preparation is as follows: the As-deposited film of different-thickness is equal

It is amorphous state, film repeatability is controlled, and film composition is consistent, structure-controllable.

Two, comparative test and interpretation of result

1, check experiment

Substantially the same manner as Example 1, difference is that the sputtering power of ZnSe alloys target is 70W, the sputtering of Ge simple substance target

Power is 0W, at room temperature sputter coating, is sputtered after thickness is about 1 μm to get the ZnSe film for arriving deposited.By the thin of preparation

Film carries out XRD and AFM performance test, and test result is as shown in figure 1 and table 1, it can be seen that film prepared by comparative examples 1

Can index it is as follows: deposited ZnSe film crystallization, ZnSe roughness (RMS) is 3.558nm, in addition, optics is taken off through spectrum

Show that transmitance is 80%, short wavelength cutoff side is 500nm.Above-mentioned control experiment and above-described embodiment 1, embodiment 2 and embodiment 3

Target as sputter power, Zn, Se, Ge content and relevant parameter are as shown in table 1.

The 1 μ m-thick Zn-Se-Ge thin-film material and relevant parameter prepared under 1 different condition of table

2, interpretation of result

The film prepared in embodiment 1, embodiment 2 and embodiment 3 is subjected to X-ray diffraction test, test result is as schemed

Shown in 1 and Fig. 2.

Fig. 1 tests the X-ray diffractogram of deposited ZnSe film.A crystallization is presented in the ZnSe film prepared at room temperature

Peak shows deposited partially crystallizable.It introduces after Ge as shown in Fig. 2, the film of the Zn-Se-Ge of deposited shows the source of an allusion

The dizzy figure of the amorphous state of type, is precipitated without crystal grain, shows that the Zn-Se-Ge film of preparation is amorphous nature.According to atomic force

Microscope testing film surface roughness is as shown in Table 1, and the roughness of ZnSe is 3.558nm, with the introducing of Ge, and sputters function

Rate is continuously increased, 70ZnSe-5Ge, and the roughness of 70ZnSe-8Ge and 70ZnSe-11Ge film is reduced to 2.316nm,

1.745nm 1.214nm.Illustrate the Zn-Se-Ge film surface uniform ground of preparation.

Fig. 3 gives ZnSe in Zn-Se-Ge, 70ZnSe-5Ge and 70ZnSe-11Ge As-deposited film penetrates spectrum.From

As can be seen that the ZnSe film transmitance with higher of deposited is 80% in figure, short wavelength cutoff side is 500nm.With Ge

Introducing, short wavelength cutoff side occurs mobile to long wave direction, moves on to 1000nm from 500nm.Transmitance is between 40-60%.

Fig. 4 gives the real-time light-induced variable of ZnSe film, as a result, it has been found that its transmitance does not occur photobleaching with wavelength

Or photodarkening phenomenon.

Fig. 5 gives the real-time light-induced variable phenomenon of the 70ZnSe-5Ge film of the preparation of embodiment 1, as a result, it has been found that it is penetrated

There is continuous photodarkening until transmitance is negative with wavelength increase in rate.

Fig. 6 gives the real-time light-induced variable phenomenon of the 70ZnSe-11Ge film of the preparation of embodiment 3, as a result, it has been found that it is thoroughly

Rate is crossed as bleaching again first occurs darkening after photobleaching in wavelength increase, shows stronger light sensitive characteristic.

The X-ray diffractogram of the 70ZnSe-11Ge film of 0.65 μm and 0.62 μ m-thick is set forth in Fig. 7 and Fig. 8, it was demonstrated that

The film of different-thickness preparation is amorphous character.

The Raman spectrogram of the 70ZnSe-11Ge film of 0.65 μm and 0.62 μ m-thick is set forth in Fig. 9 and Figure 10, it was demonstrated that

The uniform film of the component structure having the same of different-thickness preparation.

In conclusion the stability of Zn-Se-Ge thin-film material prepared by the present invention is high, roughness is low, and transmitance is higher,

Short wavelength cutoff side is shorter, and film composition deviation is small, stable structure;Preferably, it is preferred that the bis- target preparations of sputtering power 70ZnSe-11Ge

Film, that is, Zn33.4Se35.1Ge31.5, stability with higher, roughness is low, and film composition deviation is smaller, and photic variation is bright

It is aobvious.

Certainly, above description is not limitation of the present invention, and the present invention is also not limited to the example above.The art

The variations, modifications, additions or substitutions that those of ordinary skill makes within the essential scope of the present invention also should belong to protection of the present invention

Range.

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