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一种多晶光致发光钨酸锌薄膜的制备方法 【EN】A kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film

申请(专利)号:CN201711276096.4国省代码:重庆 85
申请(专利权)人:【中文】重庆理工大学【EN】Chongqing University of Technology
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摘要:
【中文】本发明公开了一种多晶光致发光钨酸锌薄膜的制备方法,采用磁控溅射的方法制备,包括如下步骤:(a)制备氧化钨薄膜层;(b)在步骤(a)的基础上制备氧化锌薄膜层;(c)在步骤(b)的基础上制备氧化钨薄膜,重复步骤(a)中的操作;(d)对上述制备的WO3/ZnO/WO3多层薄膜在空气中进行退火处理,随后自然降温,即得最终样品。本发明采用金属钨和氧化锌陶瓷作为靶材,成本低、环保,且可大规模生产,制备的多晶钨酸锌薄膜与基底结合具有优良光致发光性能和较好透明度(>70%)。 【EN】Paragraph:The invention discloses a kind of preparation methods of polycrystalline luminescence generated by light Zinc Tungstate film, are prepared using the method for magnetron sputtering, include the following steps: that (a) prepares tungsten oxide film layer;(b) zinc oxide films film layer is prepared on the basis of step (a);(c) tungsten oxide film is prepared on the basis of step (b), repeats the operation in step (a);(d) to the WO of above-mentioned preparation3/ZnO/WO3Plural layers are made annealing treatment in air, and subsequent Temperature fall is to get final sample.The present invention is used as target using tungsten and zinc oxide ceramics, at low cost, environmentally friendly, and can be mass-produced, and the polycrystalline Zinc Tungstate film of preparation is in conjunction with substrate with excellent photoluminescence performance and preferable transparency (> 70%).

主权项:
【中文】1.一种多晶光致发光钨酸锌薄膜的制备方法,其特征在于,包括如下步骤: (a)制备氧化钨薄膜层: (a1)先后用丙酮、酒精和去离子水超声清洗石英基片,用N吹干,再将清洗后的石英基片干燥30min; (a2)将金属钨靶置于磁控溅射室,所述金属钨靶的纯度为99.99%; (a3)将步骤(a1)中洁净的石英基片放入带金属钨靶的磁控溅射室,抽真空至<5×10Pa; (a4)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:15,磁控溅射室压强为4Pa; (a5)打开磁控溅射电源,将溅射功率调至为80W,开始预溅射3~10 min,石英基片不加热; (a6)通过溅射沉积时间来控制氧化钨膜层厚度,溅射沉积时间10~15min后,关闭溅射电源,使沉积的氧化钨薄膜在真空中冷却30~60min; (b)在步骤(a)的基础上制备氧化锌薄膜层: (b1)向溅射室通入N至大气压,打开溅射室,将金属钨靶换成氧化锌陶瓷靶,所述氧化锌陶瓷靶纯度为99.9%; (b2)重复上述步骤(a3)的操作; (b3)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:0~10,磁控溅射室压强为2Pa; (b4)打开磁控溅射电源,将溅射功率调至为50W,开始预溅射3~10min,石英基片不加热; (b5)通过溅射沉积时间来控制氧化锌膜层厚度,溅射沉积时间5-30min后,关闭溅射电源,使沉积的氧化锌薄膜在真空中冷却30~60min; (c)在步骤(b)的基础上制备氧化钨薄膜,重复步骤(a)中的操作; (d)对上述制备的WO/ZnO/WO多层薄膜在空气中进行退火处理,随后自然降温,即得多晶光致发光钨酸锌薄膜,其中,退火时间为30min,退火温度为450~850℃,升温速率为3℃/min。 【EN】1. a kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film, which comprises the steps of: (a) tungsten oxide film layer is prepared: (a1) successively it is cleaned by ultrasonic quartz substrate with acetone, alcohol and deionized water, uses NDrying, then by the quartzy base after cleaning Piece dries 30min; (a2) metal tungsten target is placed in magnetron sputtering chamber, the purity of the metal tungsten target is 99.99%; (a3) quartz substrate clean in step (a1) is put into the magnetron sputtering chamber with metal tungsten target, is evacuated to < 5 × 10Pa; (a4) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:15, magnetic Control sputtering chamber pressure is 4Pa; (a5) magnetron sputtering power supply is opened, sputtering power is adjusted to start 3 ~ 10 min of pre-sputtering for 80W, quartz substrate is not added Heat; (a6) it controls tungsten oxide thicknesses of layers by the sputtering sedimentation time, after 10 ~ 15min of sputtering sedimentation time, closes sputtering Power supply makes the tungsten oxide film of deposition cool down 30 ~ 60min in a vacuum; (b) zinc oxide films film layer is prepared on the basis of step (a): (b1) N is passed through to sputtering chamberTo atmospheric pressure, sputtering chamber is opened, changes metal tungsten target into zinc-oxide ceramic target, the oxidation Zinc ceramic target purity is 99.9%; (b2) repeat the above steps the operation of (a3); (b3) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:0 ~ 10, Magnetron sputtering chamber pressure is 2Pa; (b4) magnetron sputtering power supply is opened, sputtering power is adjusted to start 3 ~ 10min of pre-sputtering for 50W, quartz substrate is not added Heat; (b5) it controls zinc oxide film thickness by the sputtering sedimentation time, after sputtering sedimentation time 5-30min, closes sputtering electricity Source makes the zinc-oxide film of deposition cool down 30 ~ 60min in a vacuum; (c) tungsten oxide film is prepared on the basis of step (b), repeats the operation in step (a); (d) to the WO of above-mentioned preparation/ZnO/WOPlural layers are made annealing treatment in air, and subsequent Temperature fall is to get more Brilliant luminescence generated by light Zinc Tungstate film, wherein annealing time 30min, annealing temperature be 450 ~ 850 DEG C, heating rate be 3 DEG C/ min。


说明书

【中文】

一种多晶光致发光钨酸锌薄膜的制备方法

技术领域

本发明涉及镀膜技术领域,具体涉及一种多晶光致发光钨酸锌薄膜的制备方法。

技术背景

发光材料已广泛应用于国民经济各领域和人们的日常生活中,是照明、显示器、节能灯、辐射探测器等光电器件中不可缺少的材料。其中基于钨酸根离子(WO42-)的钨酸锌(ZnWO4)晶体是一种优良的闪烁晶体,在紫外光激发下,ZnWO4晶体可以发出强的蓝绿光,并且具有化学性能稳定、抗辐射和强光损伤能力强等优点,在激发晶体、电离辐射探测器等方面有很好的应用前景。同时随着对元器件小型化、集成化、节能化及性能要求的不断提高,利用低维(薄膜)材料制造各种元器件已是未来发展趋势。

1998年德国M. Bonanni等人(M. Bonanni, et al, Chem. Mater. 1998, 10, 304-310)利用醋酸锌和六甲酸钨的异质胶联体制备了ZnWO4薄膜,这种薄膜可以发出较强的蓝光,但其制备工艺复杂,涉及不同温度下金属有机化合物的前期脱水处理以及后续溶胶-凝胶的工艺,且制备的薄膜与衬底结合性并不理想。2003年日本Hideki Hayashi等人(Hideki Hayashi, et al, Appl. Phys. Lett. 2003, 82: 1365)利用脉冲沉积法制备了ZnO-WO3二元复合薄膜,得到了基于钨酸锌的发光薄膜,但采用这种制备方法难以实现大面积薄膜制备。2012年乌克兰A. M. Dubovik等人(A. M. Dubovik, et al, J. Phys.& Astronmy,2012, 1(1): 56)利用离子束溅射ZnWO4单晶制备了ZnWO4薄膜,在X射线辐照下发出蓝绿光,但是其溅射靶材ZnWO4单晶成本过于昂贵,且溅射过程中容易形成非计量比的ZnWO4。近年来,人们又以钨酸钠、钨酸铵、硝酸锌、醋酸锌等为原料利用溶胶-凝胶法和水热法在玻璃基片上制备了多晶ZnWO4发光薄膜,发现薄膜在270~300nm光激发下,能发出470~490nm的光,但是该种方法在制备的过程中容易引入杂质,工艺参数复杂,且较低的退火温度(<500℃)也会导致薄膜结晶度低,影响发光性能,镀膜层与基底的结合力较弱。

发明内容

针对现有技术存在的上述不足,本发明的目的是提供一种多晶光致发光钨酸锌薄膜的制备方法,以获取优良光致发光性能和较好透明度(>70%)的薄膜,同时解决现有ZnWO4单晶薄膜制备工艺苛刻、膜层与基底结合力弱以及性能优化等问题。

实现上述目的,本发明采用如下技术方案:

一种多晶光致发光钨酸锌薄膜的制备方法,其特征在于,包括如下步骤:

(a)制备氧化钨薄膜层:

(a1)先后用丙酮、酒精和去离子水超声清洗石英基片,用N2吹干,再将清洗后的石英基片干燥30min;

(a2)将金属钨靶置于磁控溅射室,所述金属钨靶的纯度为99.99%;

(a3)将步骤(a1)中洁净的石英基片放入带金属钨靶的磁控溅射室,抽真空至<5×10-4Pa;

(a4)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:15,磁控溅射室压强为4Pa;

(a5)打开磁控溅射电源,将溅射功率调至为80W,开始预溅射3~10 min,石英基片不加热;

(a6)通过溅射沉积时间来控制氧化钨膜层厚度,溅射沉积时间10~15min后,关闭溅射电源,使沉积的氧化钨薄膜在真空中冷却30~60min;

(b)在步骤(a)的基础上制备氧化锌薄膜层:

(b1)向溅射室通入N2至大气压,打开溅射室,将金属钨靶换成氧化锌陶瓷靶,所述氧化锌陶瓷靶纯度为99.9%;

(b2)重复上述步骤(a3)的操作;

(b3)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:0~10,磁控溅射室压强为2Pa;

(b4)打开磁控溅射电源,将溅射功率调至为50W,开始预溅射3~10min。石英基片不加热;

(b5)通过溅射沉积时间来控制氧化锌膜层厚度,溅射沉积时间5-30min后,关闭溅射电源,使沉积的氧化锌薄膜在真空中冷却30~60min;

(c)在步骤(b)的基础上制备氧化钨薄膜,重复步骤(a)中的操作;

(d)对上述制备的WO3/ZnO/WO3多层薄膜在空气中进行退火处理,随后自然降温,即得多晶光致发光钨酸锌薄膜。

相比现有技术,本发明具有如下有益效果:

1、本发明采用磁控溅射方法制备了基于ZnO和WO3三明治结构的异质薄膜,该异质薄膜在空气中退火处理后即可获得具有优良光致发光性能和较好透明度(>70%)的多晶钨酸锌薄膜,其发光性能是通过控制WO3、ZnO沉积厚度、退火温度来实现的。

2、相对现有ZnWO4单晶薄膜的制备方法,本发明利用常规的金属钨和氧化锌陶瓷作为靶材,成功制备出发光性能优良的多晶钨酸锌薄膜的同时,也解决了现有制备方法工艺苛刻、成本高等问题。

3、采用本发明的方法制备出的多晶钨酸锌薄膜在紫外光激发下可以发出强的蓝绿光,退火温度为750℃时制备出的多晶钨酸锌薄膜结晶度高、平整无裂纹,具有纳米结构。

4、本发明的制备的工艺简单、工艺参数易于可控;由于薄膜通过磁控溅射过程中产生的高能粒子与基底碰撞而形成,所以膜层与基底的结合力较强;可以实现大面积、大规模生产。

5、本发明不仅为制备多晶ZnWO4提供了一种方法和途径,也进一步发掘了ZnWO4薄膜的发光性能,为发展基于多晶ZnWO4的发光薄膜和光电探测器等应用提供了实验依据。

附图说明

图1为沉积WO3层时不同沉积时间对退火后发光薄膜荧光强度的影响;

图2为沉积ZnO层时改变氩气和氧气的体积流量比对退火后发光薄膜强度的影响;

图3为沉积ZnO层时不同沉积时间对退火后发光薄膜荧光强度的影响;

图4为不同退火温度对发光薄膜荧光强度的影响;

图5为不同退火温度下制备的薄膜的XRD图;

图6为不同退火温度下制备的薄膜的Raman谱图;

图7为薄膜样品的SEM图:(a)退火前薄膜SEM图,(b)退火后薄膜SEM图,

(c)退火温度为750℃时的SEM图,(d)退火温度为850℃时的SEM图;

图8为不同退火温度下制备的薄膜的UV-Vis透射光谱图。

具体实施方式

下面结合具体实施例和附图对本发明作进一步详细说明。本实验中对退火后的样品进行光致发光性能测试采用的荧光光度计型号为F-4600,Hitachi。

一、本发明多晶光致发光钨酸锌薄膜的制备方法

实施例1

一种多晶光致发光钨酸锌薄膜的制备方法,包括如下步骤:

(a)制备氧化钨薄膜层:

(a1)先后用丙酮、酒精和去离子水超声清洗石英基片,用N2吹干,再将清洗后的石英基片干燥30min;

(a2)将金属钨靶置于磁控溅射室,所述金属钨靶的纯度为99.99%;

(a3)将步骤(a1)中洁净的石英基片放入带金属钨靶的磁控溅射室,抽真空至<5×10-4Pa;

(a4)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:15,磁控溅射室压强为4Pa;

(a5)打开磁控溅射电源,将溅射功率调至为80W,开始预溅射3~10 min,石英基片不加热;

(a6)通过溅射沉积时间来控制氧化钨膜层厚度,溅射沉积时间10min后,关闭溅射电源,使沉积的氧化钨薄膜在真空中冷却60min;

(b)在步骤(a)的基础上制备氧化锌薄膜层:

(b1)向溅射室通入N2至大气压,打开溅射室,将金属钨靶换成氧化锌陶瓷靶,所述氧化锌陶瓷靶纯度为99.9%;

(b2)重复上述步骤(a3)的操作;

(b3)向上述磁控溅射室中通入氩气和氧气,调节氩气和氧气的体积流量比为20:6,磁控溅射室压强为2Pa;

(b4)打开磁控溅射电源,将溅射功率调至为50W,开始预溅射3~10min。石英基片不加热;

(b5)通过溅射沉积时间来控制氧化锌膜层厚度,溅射沉积时间10min后,关闭溅射电源,使沉积的氧化锌薄膜在真空中冷却60min;

(c)在步骤(b)的基础上制备氧化钨薄膜,重复步骤(a)中的操作;

(d)将多层薄膜从溅射室中取出,放入马弗炉中,在空气中退火30min,退火温度为750℃,升温速率为3℃/min,随后自然降温,即得多晶光致发光钨酸锌薄膜。

实施例2

实验方法同实施例1,其他条件不变,步骤(a6)中溅射沉积时间设为变量,分别为10min和15min,结果如图1所示。

从图1可以看出,固定沉积ZnO层的条件,退火条件为:退火温度为750℃,保温时间30min,升温速率为3℃/min的情况下,当WO3的沉积时间为15min时,同样测试条件下,用285nm左右的光激发,所获得样品的发射光谱峰值明显增,为WO3沉积10min样品的2.5倍。

实施例3

实验方法同实施例1,其他条件不变,步骤(b3)中调节氩气和氧气的体积流量比设为变量,分别为20:0、20:3、20:6和20:10,结果如图2所示。

从图2可以看出,固定沉积WO3层的条件,退火条件为:退火温度为750℃,保温时间30min,升温速率为3℃/min的情况下,当氩气和氧气的体积流量比为20:6时,同样测试条件下,用285nm左右的光激发,所获得样品的发射光谱强度最强,但当氩气和氧气的体积流量比为20:10时,所获得的样品发光强度明显降低,甚至低于无氧溅射时样品的发光强度,说明反应溅射过程中氧气成分不能过高,氩氧体积流量比应该控制在大于20:10的范围,氧气流量不能太大。

实施例4

实验方法同实施例1,其他条件不变,步骤(b5)中溅射沉积时间设为变量,分别为5min、10min、15min、20min和30min,结果如图3所示。

从图3可以看出,固定沉积WO3层的条件,退火条件为:退火温度为750℃,保温时间30min,升温速率为3℃/min的情况下,当溅射沉积时间为15min和20min时,同样测试条件下,用285nm左右的光激发样品时发光谱强度最大,其中溅射15min的样品发射光谱中心波长为490nm,半高宽约120nm;而溅射20min的样品发射光谱中心波长为460nm,半高宽约105nm。

实施例5

实验方法同实施例1,其他条件不变,步骤(d)中退火温度设为变量,分别为450oC、650℃、750℃和850℃,结果如图4所示。

从图中可以看出,固定WO3层和ZnO层的沉积时间均为10min的情况下,当退火温度为750℃时,同样测试条件下,用285nm左右的光激发样品时,所获得的样品发射光谱强度最佳,中心波长为465nm;在650℃和850℃退火后样品的发射光谱中心波长则在473nm左右。

二、多晶光致发光钨酸锌薄膜的成分、形貌和UV-Vis透射光谱

1、X-射线衍射仪(XRD)测试

为了研究所制备的薄膜样品成分和晶体结构,对退火后的薄膜进行了XRD测试,其中WO3层和ZnO层沉积时间均为10min,从图5中可以看出本发明所制备的薄膜样品的XRD图谱与标准ZnWO4粉末衍射的单斜相图谱(PDF#-0774)吻合,且随着退火温度的升高,薄膜样品的结晶度明显提高。

共焦Raman光谱测试

为了研究所制备的薄膜样品晶格振动模式,对退火后的薄膜进行了共焦Raman光谱分析,其中WO3层和ZnO层沉积时间均为10min,从图6中可知本发明所制备的样品为主要为钨酸锌晶格振动模式。

2、扫描电子显微镜(SEM)测试

为了研究所制备的薄膜样品表面形貌,对退火后的薄膜进行了SEM测试,其中WO3层和ZnO层沉积时间均为10min,(a)中退火前薄膜厚度约250nm,(b)中退火后薄膜厚度约800nm,(c)中退火温度为750℃,(d)中退火温度为850℃,从图7可以看出,当退火温度由750oC升高为到850oC时,薄膜表面形貌由平整的纳米结构变为粗糙的纳米结构,晶粒大小明显增大;可见退火温度为750℃为

最佳的退火处理温度,在该温度下制备的薄膜样品具有平整、均匀的纳米结构。

3、UV-Vis透射光谱测试

为了研究所制备的薄膜样品的光学吸收特性,利用UV-Vis分光光度计对退火后的薄膜进行了UV-Vis透射光谱的测试,其中WO3层和ZnO层沉积时间均为10min,从图8中可以知道,退火温度为750℃时,本发明所制备的薄膜样品透射率大于70%,这说明采用本发明的方法制备的薄膜具有较好的透明度。此外薄膜有两个明显的透射上升沿,分别位于350nm和270nm左右,其中位于270nm左右的吸收应该为发光吸收。

由此可见,利用磁控溅射的方法在石英基片上沉积了WO3/ZnO/WO3异质多层薄膜,该薄膜退火后具有良好的光致发光性能,发射光谱中心波长为460-490nm,光谱半高宽达105-120nm。经分析表明:退火后的薄膜主要成分为单斜相的ZnWO4;制备最佳发光性能薄膜的制备条件为:WO3层沉积时间为15min,ZnO的沉积时间为15-20min,在沉积ZnO时,Ar/O2体积流量比为20:6左右,在750oC温度下,退火保温30min,升温速率为3oC/min。本发明不仅为制备多晶ZnWO4提供了一种方法和途径,也进一步发掘了ZnWO4薄膜的发光性能,为发展基于多晶ZnWO4的发光薄膜和光电探测器等应用提供了实验依据。

最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。

【EN】

A kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film

Technical field

The present invention relates to coating technique fields, and in particular to a kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film.

Technical background

Luminescent material is widely used in all fields of national economy and daily life, is illumination, display, section

Indispensable material in the photoelectric devices such as energy lamp, radiation detector.Wherein it is based on tungstate ion (WO42-) Zinc Tungstate

(ZnWO4) crystal is a kind of excellent scintillation crystal, under ultraviolet excitation, ZnWO4Crystal can issue strong blue green light, and

And have many advantages, such as that stable chemical performance, anti-radiation and strong light injury ability are strong, in sides such as excitation crystal, ionizing radiation detectors

There is good application prospect in face.Simultaneously with component is minimized, the continuous improvement of integrated, energy-saving and performance requirement,

Manufacturing various components using low-dimensional (film) material has been future developing trend.

Germany M. Bonanni in 1998 et al. (M. Bonanni, et al,Chem. Mater. 1998, 10,

304-310) conjuncted ZnWO is prepared for using the heterogeneous glue of zinc acetate and pregnancy acid tungsten4Film, this film can issue relatively strong

Blue light, but its preparation process is complicated, is related under different temperatures metal-organic dehydration early period and subsequent molten

Glue-gel technique, and the film and substrate associativity that prepare are unsatisfactory.Japan Hideki Hayashi in 2003 et al.

(Hideki Hayashi, et al,Appl. Phys. Lett.2003,82:1365) it is prepared for using pulsed deposition method

ZnO-WO3Binary laminated film has obtained the light-emitting film based on Zinc Tungstate, but has been difficult to realize big face using this preparation method

Product film preparation.Ukraine A. M. Dubovik in 2012 et al. (A. M. Dubovik, et al,J. Phys.& Astronmy,2012,1 (1): ion beam sputtering ZnWO 56) is utilized4Single crystal preparation ZnWO4Film is issued in x-ray irradiation

Blue green light out, but its sputtering target material ZnWO4Monocrystalline cost is prohibitively expensive, and non-metering ratio easy to form in sputtering process

ZnWO4.In recent years, people are again that raw material utilizes sol-gel method and hydro-thermal with sodium tungstate, ammonium tungstate, zinc nitrate, zinc acetate etc.

Method is prepared for polycrystalline ZnWO on a glass substrate4Light-emitting film, discovery film under the excitation of 270 ~ 300nm light, can issue 470 ~

The light of 490nm, but this kind of method is readily incorporated impurity during preparation, technological parameter is complicated, and lower annealing temperature

It is low that degree (< 500 DEG C) also results in film crystal unity, influences luminescent properties, and the binding force of film plating layer and substrate is weaker.

Summary of the invention

In view of the above shortcomings of the prior art, the object of the present invention is to provide a kind of polycrystalline luminescence generated by light Zinc Tungstate is thin

The preparation method of film to obtain the film of excellent photoluminescence performance and preferable transparency (> 70%), while solving existing ZnWO4

Monocrystal thin films preparation processes is harsh, film layer and the problems such as substrate caking power is weak and performance optimizes.

Realize above-mentioned purpose, the present invention adopts the following technical scheme:

A kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film, which comprises the steps of:

(a) tungsten oxide film layer is prepared:

(a1) successively it is cleaned by ultrasonic quartz substrate with acetone, alcohol and deionized water, uses N2Drying, then by the stone after cleaning

English substrate dries 30min;

(a2) metal tungsten target is placed in magnetron sputtering chamber, the purity of the metal tungsten target is 99.99%;

(a3) quartz substrate clean in step (a1) is put into the magnetron sputtering chamber with metal tungsten target, it is evacuated to < 5 ×

10-4Pa;

(a4) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:

15, magnetron sputtering chamber pressure is 4Pa;

(a5) magnetron sputtering power supply is opened, sputtering power is adjusted to as 80W, beginning 3 ~ 10 min of pre-sputtering, quartz substrate

It does not heat;

(a6) it controls tungsten oxide thicknesses of layers by the sputtering sedimentation time, after 10 ~ 15min of sputtering sedimentation time, closes

Shielding power supply makes the tungsten oxide film of deposition cool down 30 ~ 60min in a vacuum;

(b) zinc oxide films film layer is prepared on the basis of step (a):

(b1) N2 is passed through to atmospheric pressure to sputtering chamber, opening sputtering chamber changes metal tungsten target into zinc-oxide ceramic target, described

Zinc-oxide ceramic target purity is 99.9%;

(b2) repeat the above steps the operation of (a3);

(b3) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:0

~ 10, magnetron sputtering chamber pressure is 2Pa;

(b4) magnetron sputtering power supply is opened, sputtering power is adjusted to as 50W, beginning 3 ~ 10min of pre-sputtering.Quartz substrate is not

Heating;

(b5) zinc oxide film thickness is controlled by the sputtering sedimentation time, after sputtering sedimentation time 5-30min, closing is splashed

Radio source makes the zinc-oxide film of deposition cool down 30 ~ 60min in a vacuum;

(c) tungsten oxide film is prepared on the basis of step (b), repeats the operation in step (a);

(d) to the WO of above-mentioned preparation3/ZnO/WO3Plural layers are made annealing treatment in air, subsequent Temperature fall, i.e.,

Obtain polycrystalline luminescence generated by light Zinc Tungstate film.

Compared with prior art, the invention has the following beneficial effects:

1, the present invention is prepared for using magnetically controlled sputter method based on ZnO and WO3The heterofilm of sandwich structure, this is heterogeneous

Film can be obtained the polycrystalline tungsten with excellent photoluminescence performance and preferable transparency (> 70%) after making annealing treatment in air

Sour zinc film, luminescent properties are by controlling WO3, ZnO deposition thickness, annealing temperature realize.

2, relatively existing ZnWO4The preparation method of monocrystal thin films, the present invention utilize conventional tungsten and zinc oxide ceramics

As target, while successfully preparing the polycrystalline Zinc Tungstate film of good luminescence property, also solves existing preparation method work

The problems such as skill is harsh, at high cost.

3, the polycrystalline Zinc Tungstate film prepared using method of the invention can issue strong indigo plant under ultraviolet excitation

Green light, polycrystalline Zinc Tungstate film crystal unity height, the smooth flawless that annealing temperature is prepared when being 750 DEG C, has nanostructure.

4, the simple process of preparation of the invention, technological parameter are easy to controllable;Since film passes through in magnetron sputtering process

The high energy particle of generation is formed with Basement collision, so the binding force of film layer and substrate is stronger;Large area, big rule may be implemented

Mould production.

5, the present invention is not only to prepare polycrystalline ZnWO4It provides a method and approach, has also further excavated ZnWO4It is thin

The luminescent properties of film are based on polycrystalline ZnWO for development4Light-emitting film and the application such as photodetector provide experimental basis.

Detailed description of the invention

Fig. 1 is deposition WO3Influence of the difference sedimentation time to light-emitting film fluorescence intensity after annealing when layer;

Fig. 2 is the influence that the volume flow of change argon gas and oxygen compares light-emitting film intensity after annealing when depositing ZnO layer;

Fig. 3 is influence of the difference sedimentation time to light-emitting film fluorescence intensity after annealing when depositing ZnO layer;

Fig. 4 is influence of the different annealing temperature to light-emitting film fluorescence intensity;

Fig. 5 is the XRD diagram of the film prepared under different annealing temperature;

Fig. 6 is the Raman spectrogram of the film prepared under different annealing temperature;

Fig. 7 is that the SEM of film sample schemes: film SEM figure before (a) annealing, rear film SEM figure of (b) annealing,

(c) SEM figure when annealing temperature is 750 DEG C, SEM figure when (d) annealing temperature is 850 DEG C;

Fig. 8 is the UV-Vis transmitted light spectrogram of the film prepared under different annealing temperature.

Specific embodiment

Invention is further described in detail with attached drawing combined with specific embodiments below.To the sample after annealing in this experiment

Product carry out fluophotometer the model F-4600, Hitachi that photoluminescence performance test uses.

One, the preparation method of polycrystalline luminescence generated by light Zinc Tungstate film of the present invention

Embodiment 1

A kind of preparation method of polycrystalline luminescence generated by light Zinc Tungstate film, includes the following steps:

(a) tungsten oxide film layer is prepared:

(a1) successively it is cleaned by ultrasonic quartz substrate with acetone, alcohol and deionized water, uses N2Drying, then by the stone after cleaning

English substrate dries 30min;

(a2) metal tungsten target is placed in magnetron sputtering chamber, the purity of the metal tungsten target is 99.99%;

(a3) quartz substrate clean in step (a1) is put into the magnetron sputtering chamber with metal tungsten target, it is evacuated to < 5 ×

10-4Pa;

(a4) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:

15, magnetron sputtering chamber pressure is 4Pa;

(a5) magnetron sputtering power supply is opened, sputtering power is adjusted to as 80W, beginning 3 ~ 10 min of pre-sputtering, quartz substrate

It does not heat;

(a6) it controls tungsten oxide thicknesses of layers by the sputtering sedimentation time, after sputtering sedimentation time 10min, closes sputtering

Power supply makes the tungsten oxide film of deposition cool down 60min in a vacuum;

(b) zinc oxide films film layer is prepared on the basis of step (a):

(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal tungsten target into zinc-oxide ceramic target, it is described

Zinc-oxide ceramic target purity is 99.9%;

(b2) repeat the above steps the operation of (a3);

(b3) argon gas and oxygen are passed through in Xiang Shangshu magnetron sputtering chamber, the volume flow ratio for adjusting argon gas and oxygen is 20:

6, magnetron sputtering chamber pressure is 2Pa;

(b4) magnetron sputtering power supply is opened, sputtering power is adjusted to as 50W, beginning 3 ~ 10min of pre-sputtering.Quartz substrate is not

Heating;

(b5) it controls zinc oxide film thickness by the sputtering sedimentation time, after sputtering sedimentation time 10min, closes sputtering

Power supply makes the zinc-oxide film of deposition cool down 60min in a vacuum;

(c) tungsten oxide film is prepared on the basis of step (b), repeats the operation in step (a);

(d) plural layers are taken out from sputtering chamber, is put into Muffle furnace, anneal 30min in air, and annealing temperature is

750 DEG C, heating rate is 3 DEG C/min, and subsequent Temperature fall is to get polycrystalline luminescence generated by light Zinc Tungstate film.

Embodiment 2

For experimental method with embodiment 1, other conditions are constant, and the sputtering sedimentation time is set as variable in step (a6), respectively

10min and 15min, as a result as shown in Figure 1.

It will be seen from figure 1 that the condition of fixed deposition ZnO layer, annealing conditions are as follows: annealing temperature is 750 DEG C, soaking time

30min works as WO in the case that heating rate is 3 DEG C/min3Sedimentation time when being 15min, under same test condition, use

The light of 285nm or so excites, and the Emission Spectrum Peals of obtained sample obviously increase, and is WO3Deposit 2.5 times of 10min sample.

Embodiment 3

For experimental method with embodiment 1, other conditions are constant, and argon gas is adjusted in step (b3) and the volume flow ratio of oxygen is set

For variable, respectively 20:0,20:3,20:6 and 20:10, as a result as shown in Figure 2.

Figure it is seen that fixed deposition WO3The condition of layer, annealing conditions are as follows: annealing temperature is 750 DEG C, soaking time

30min, in the case that heating rate is 3 DEG C/min, when the volume flow ratio of argon gas and oxygen is 20:6, same test condition

Under, it is excited with the light of 285nm or so, the intensity of emission spectra of obtained sample is most strong, but works as the volume flow of argon gas and oxygen

When than for 20:10, sample luminous intensity obtained is substantially reduced, even lower than oxygen-free sputtering when sample luminous intensity, say

Oxygen gas component cannot be excessively high in bright reactive sputtering process, and argon oxygen volume flow ratio should be controlled in the range for being greater than 20:10, oxygen

Flow cannot be too big.

Embodiment 4

For experimental method with embodiment 1, other conditions are constant, and the sputtering sedimentation time is set as variable in step (b5), respectively

5min, 10min, 15min, 20min and 30min, as a result as shown in Figure 3.

From figure 3, it can be seen that fixed deposition WO3The condition of layer, annealing conditions are as follows: annealing temperature is 750 DEG C, soaking time

30min, in the case that heating rate is 3 DEG C/min, when the sputtering sedimentation time is 15min and 20min, same test condition

Under, luminous spectrum maximum intensity when exciting sample with the light of 285nm or so, wherein cardiac wave in the electromagnetic radiation spectrum of sputtering 15min

A length of 490nm, halfwidth about 120nm;And the electromagnetic radiation spectrum central wavelength for sputtering 20min is 460nm, halfwidth is about

105nm。

Embodiment 5

For experimental method with embodiment 1, other conditions are constant, and annealing temperature is set as variable, respectively 450 in step (d)oC、

650 DEG C, 750 DEG C and 850 DEG C, as a result as shown in Figure 4.

It can be seen from the figure that fixed WO3In the case that layer and the sedimentation time of ZnO layer are 10min, work as annealing temperature

When being 750 DEG C, under same test condition, when exciting sample with the light of 285nm or so, electromagnetic radiation spectrum intensity obtained is most

It is good, central wavelength 465nm;The emission spectrum central wavelength of sample is then in 473nm or so after 650 DEG C and 850 DEG C annealing.

Two, the ingredient of polycrystalline luminescence generated by light Zinc Tungstate film, pattern and UV-Vis transmitted spectrum

1, x-ray diffractometer (XRD) is tested

In order to study prepared film sample ingredient and crystal structure, XRD test has been carried out to the film after annealing,

Middle WO3Layer and ZnO layer sedimentation time are 10min, as can be seen from Figure 5 the XRD diagram of the film sample prepared by the present invention

Spectrum and standard ZnWO4The monoclinic phase map (PDF#-0774) of powder diffraction coincide, and with the raising of annealing temperature, film sample

The crystallinity of product significantly improves.

Confocal Raman spectrum test

In order to study prepared film sample lattice vibration mode, confocal Raman light has been carried out to the film after annealing

Spectrum analysis, wherein WO3Layer and ZnO layer sedimentation time are 10min, and the sample prepared by the present invention is main as can be known from Fig. 6

For Zinc Tungstate lattice vibration mode.

2, scanning electron microscope (SEM) is tested

In order to study prepared film sample surface topography, SEM test is carried out to the film after annealing, wherein WO3

Layer and ZnO layer sedimentation time are 10min, film thickness about 250nm before annealing in (a), (b) in annealing rear film thickness about

800nm, (c) in annealing temperature be 750 DEG C, (d) in annealing temperature be 850 DEG C, from figure 7 it can be seen that when annealing temperature by

750oIt is to 850 that C, which is increased,oWhen C, film surface appearance becomes coarse nanostructure from smooth nanostructure, and grain size is bright

It is aobvious to increase;It can be seen that annealing temperature is 750 DEG C is

Optimal annealing temperature, the film sample prepared at such a temperature have smooth, uniform nanostructure.

3, UV-Vis transmitted spectrum is tested

In order to study the optical absorption characteristic of prepared film sample, using UV-Vis spectrophotometer to annealing after

Film has carried out the test of UV-Vis transmitted spectrum, wherein WO3Layer and ZnO layer sedimentation time are 10min, can be with from Fig. 8

Know, when annealing temperature is 750 DEG C, film sample transmissivity prepared by the present invention is greater than 70%, this explanation is using of the invention

The film of method preparation has preferable transparency.This outer film there are two apparent transmission rising edge, be located at 350nm and

270nm or so, wherein being located at the absorption of 270nm or so should absorb to shine.

It can be seen that the method using magnetron sputtering deposited WO on quartz substrate3/ZnO/WO3Heterogenous multilayer film,

There is good photoluminescence performance, emission spectrum central wavelength is 460-490nm, and spectrum halfwidth reaches after the Thin-film anneal

105-120nm.Through analysis shows: film main component after annealing is the ZnWO of monoclinic phase4;Prepare optimal luminescent performance film

Preparation condition are as follows: WO3Layer sedimentation time is 15min, and the sedimentation time of ZnO is 15-20min, when depositing ZnO, Ar/O2Body

Product flow-rate ratio is 20:6 or so, 750oAt a temperature of C, annealing heat preservation 30min, heating rate 3oC/min.The present invention is not only

Prepare polycrystalline ZnWO4It provides a method and approach, has also further excavated ZnWO4The luminescent properties of film are based on for development

Polycrystalline ZnWO4Light-emitting film and the application such as photodetector provide experimental basis.

Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with

Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention

Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this

In the scope of the claims of invention.

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