CN108149210B - A kind of preparation method of long-wave infrared antireflection protective film - Google Patents
A kind of preparation method of long-wave infrared antireflection protective film Download PDFInfo
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Abstract
一种长波红外增透保护膜的制备方法，本发明涉及增透保护膜的制备方法。本发明要解决现有红外探测系统窗口材料增透保护膜或存在服役过程中出现严重的性能退化现象，导致薄膜光学性能的下降，或存在增透保护膜与基底附着性差，需要沉积过渡层，增加了工艺的复杂性，或存在增透保护膜硬度较低的问题。方法：一、靶材和窗口的清洗；二、镀膜前准备工作；三、采用反应溅射的方式制备Gd2O3薄膜；四、结束关机；五、双面镀膜，即完成一种长波红外增透保护膜的制备方法。本发明用于长波红外增透保护膜的制备方法。
The invention relates to a preparation method of a long-wave infrared antireflection protective film, and the invention relates to a preparation method of an antireflection protective film. The present invention aims to solve the problem of serious performance degradation of the anti-reflection protective film of the window material of the existing infrared detection system or during the service process, resulting in a decrease in the optical performance of the film, or the existence of poor adhesion between the anti-reflection protective film and the substrate, and a transition layer needs to be deposited. The complexity of the process is increased, or there is a problem of low hardness of the antireflection protective film. Methods: 1. Cleaning of the target and window; 2. Preparatory work before coating; 3. Preparation of Gd 2 O 3 thin film by reactive sputtering; 4. Finish shutdown; The preparation method of the anti-reflection protective film. The invention is used for the preparation method of the long-wave infrared antireflection protective film.
Description
技术领域technical field
本发明涉及增透保护膜的制备方法。The invention relates to a preparation method of an antireflection protective film.
背景技术Background technique
红外探测系统在探测红外信号时，因基底材料的透过率较低(小于70％)，尤其在长波红外波段(8μm～12μm)，使得探测的信号较弱，成像效果差，直接影响信号的收集和后续执行的准确性。为了提高红外波段的透过率，需在表面镀制增透膜层，提高透过率。除此之外，作为探测器的窗口材料，也需要具有一定的硬度来保护较软的基底材料。目前常用的红外窗口基底材料为ZnS，对于其增透保护主要膜系有DLC膜、碳化物、氧化物、磷化物、氮化物以及氟化物等。其中DLC、碳化锗(GexC1-x)及磷化硼(BP)等透过率经过设计后均能达到90％且硬度较高，但是薄膜在服役条件下不可避免地会出现严重的性能退化现象，导致薄膜光学性能的下降，透过率降低到60％以下。主要原因是薄膜在制备过程中由于前驱体含有H键，导致光吸收增大。同时DLC薄膜与硫化锌附着性差，需要沉积过渡层，增加了工艺的复杂性；而GexC1-x虽然具有低吸收和低应力的特点，但是与硫化锌衬底原子半径失配度大，与衬底不能形成有效的结合，利用压力为4.9N外裹脱脂棉的橡皮摩擦50次出现明显的划痕。而磷化物的前驱体材料往往具有剧毒，限制其应用。因此氧化物体系具有无毒、稳定性高等优势，目前常用的长波红外材料为氧化钇，其透过率可达90％以上，但是其硬度较低，纳米压痕硬度约为4GPa，与硫化锌基底相当。When the infrared detection system detects infrared signals, due to the low transmittance of the substrate material (less than 70%), especially in the long-wave infrared band (8 μm to 12 μm), the detected signal is weak and the imaging effect is poor, which directly affects the signal quality. Accuracy of collection and subsequent execution. In order to increase the transmittance in the infrared band, it is necessary to coat the surface with an anti-reflection coating to increase the transmittance. In addition, as the window material of the detector, it also needs to have a certain hardness to protect the softer substrate material. At present, the commonly used infrared window substrate material is ZnS, and the main film systems for its anti-reflection protection include DLC film, carbide, oxide, phosphide, nitride, and fluoride. Among them, the transmittance of DLC, germanium carbide (Gex C 1-x ) and boron phosphide (BP) can reach 90% after design, and the hardness is relatively high, but the film will inevitably appear serious damage under service conditions. The performance degradation phenomenon leads to the decrease of the optical performance of the film, and the transmittance is reduced to below 60%. The main reason is that the light absorption increases due to the precursor containing H bonds during the preparation of the film. At the same time, the DLC film has poor adhesion to zinc sulfide, and a transition layer needs to be deposited, which increases the complexity of the process; while Ge x C 1-x has the characteristics of low absorption and low stress, but has a large atomic radius mismatch with the zinc sulfide substrate , and the substrate cannot form an effective combination, and the rubber with a pressure of 4.9N wrapped in absorbent cotton is rubbed 50 times and obvious scratches appear. However, the precursor materials of phosphides are often highly toxic, which limits their applications. Therefore, the oxide system has the advantages of non-toxicity and high stability. At present, the commonly used long-wave infrared material is yttrium oxide, and its transmittance can reach more than 90%, but its hardness is low, and the nano-indentation hardness is about 4GPa. The base is comparable.
发明内容Contents of the invention
本发明要解决现有红外探测系统窗口材料增透保护膜或存在服役过程中出现严重的性能退化现象，导致薄膜光学性能的下降，或存在增透保护膜与基底附着性差，需要沉积过渡层，增加了工艺的复杂性，或存在增透保护膜硬度较低的问题，而提供一种长波红外增透保护膜的制备方法。The present invention aims to solve the problem of serious performance degradation of the anti-reflection protective film of the window material of the existing infrared detection system or during the service process, resulting in a decrease in the optical performance of the film, or the existence of poor adhesion between the anti-reflection protective film and the substrate, and a transition layer needs to be deposited. The complexity of the process is increased, or there is a problem of low hardness of the anti-reflection protective film, and a preparation method of the long-wave infrared anti-reflection protective film is provided.
一种长波红外增透保护膜的制备方法是按以下步骤完成的：A preparation method of a long-wave infrared anti-reflection protective film is completed according to the following steps:
一、靶材和窗口的清洗：1. Cleaning of targets and windows:
在超声功率为100W～300W的条件下，将金属Gd靶材依次置于丙酮、酒精和去离子水中分别清洗10min～20min，然后用氮气吹除表面附着的灰尘，得到洁净靶材；在超声功率为100W～300W的条件下，将ZnS红外窗口材料依次置于丙酮、酒精和去离子水中分别清洗10min～20min，然后用氮气吹除表面附着的灰尘，得到衬底材料；Under the condition of ultrasonic power of 100W-300W, put the metal Gd target in acetone, alcohol and deionized water for 10min-20min respectively, and then use nitrogen to blow off the dust attached to the surface to obtain a clean target; Under the condition of 100W ~ 300W, put the ZnS infrared window material in acetone, alcohol and deionized water for 10min ~ 20min, respectively, and then blow off the dust attached to the surface with nitrogen to obtain the substrate material;
二、镀膜前准备工作：2. Preparatory work before coating:
首先将洁净靶材安装至磁控溅射靶位上，并将衬底材料置于高真空磁控溅射镀膜系统内的加热台中心位置，然后启动真空系统将真空仓内抽成真空，使得真空度为6.5×10-5Pa～5.0×10-4Pa，再启动加热装置，加热衬底材料温度至200℃～700℃；First install the clean target on the magnetron sputtering target position, and place the substrate material at the center of the heating table in the high-vacuum magnetron sputtering coating system, and then start the vacuum system to evacuate the vacuum chamber so that The degree of vacuum is 6.5×10 -5 Pa～5.0×10 -4 Pa, then start the heating device, and heat the temperature of the substrate material to 200℃～700℃;
三、采用反应溅射的方式制备Gd2O3薄膜：3. Preparation of Gd 2 O 3 thin films by reactive sputtering:
调节氩气气体流量为10sccm～100sccm，调节氧气气体流量为2sccm～10sccm，偏压为-50V～-200V，将真空仓内气体压强调节至0.2Pa～2.0Pa，然后在氩气气体流量为10sccm～100sccm、氧气气体流量为2sccm～10sccm、偏压为-50V～-200V、气体压强为0.2Pa～2.0Pa及衬底材料温度为200℃～700℃的条件下，采用射频电源或高能脉冲电源溅射镀膜；Adjust the flow rate of argon gas to 10sccm~100sccm, adjust the flow rate of oxygen gas to 2sccm~10sccm, the bias voltage to -50V~-200V, adjust the gas pressure in the vacuum chamber to 0.2Pa~2.0Pa, and then adjust the flow rate of argon gas to 10sccm Under the conditions of ～100sccm, oxygen gas flow rate of 2sccm～10sccm, bias voltage of -50V～-200V, gas pressure of 0.2Pa～2.0Pa and substrate material temperature of 200℃～700℃, RF power supply or high-energy pulse power supply is used sputter coating;
当采用射频电源时，溅射功率为50W～200W，先预溅射5min～10min，然后向衬底材料表面镀膜2h～6h；当采用高能脉冲电源时，溅射功率为50W～200W，脉冲频率为10Hz～2000Hz，脉宽20μ～100μ，先预溅射5min～10min，然后向衬底材料表面镀膜2h～6h；When using a radio frequency power supply, the sputtering power is 50W-200W, pre-sputtering for 5min-10min, and then coating the surface of the substrate material for 2h-6h; when using a high-energy pulse power supply, the sputtering power is 50W-200W, pulse frequency 10Hz~2000Hz, pulse width 20μ~100μ, pre-sputter for 5min~10min, and then coat the surface of the substrate material for 2h~6h;
四、结束关机：4. End shutdown:
关闭所有电源并将真空仓内温度降至25℃～70℃，得到单面镀有Gd2O3薄膜的衬底材料；所述的Gd2O3薄膜的厚度为500nm～1500nm；Turn off all power sources and lower the temperature in the vacuum chamber to 25°C-70°C to obtain a substrate material coated with a Gd 2 O 3 film on one side; the thickness of the Gd 2 O 3 film is 500nm-1500nm;
五、双面镀膜：Five, double-sided coating:
将单面镀有Gd2O3薄膜的衬底材料未镀膜的一面按步骤二至步骤四重复进行，得到双面镀有Gd2O3薄膜的衬底材料，即完成一种长波红外增透保护膜的制备方法。Repeat step 2 to step 4 on the uncoated side of the substrate material coated with Gd 2 O 3 film on one side to obtain a substrate material coated with Gd 2 O 3 film on both sides, that is, to complete a long-wave infrared anti-reflection Preparation method of protective film.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明通过在ZnS红外窗口表面镀制具有增透和保护作用的Gd2O3薄膜，提高了红外透过率，提高探测的准确性，并对红外窗口起到保护的作用，提高硬度进而提高其抗沙蚀雨蚀性能。1. The present invention improves the infrared transmittance, improves the accuracy of detection, and protects the infrared window by coating the Gd 2 O 3 film with anti-reflective and protective effects on the surface of the ZnS infrared window, and improves the hardness And then improve its anti-sand erosion and rain erosion performance.
2、与现有的技术相比，用本发明在ZnS红外窗口上制备的Gd2O3薄膜，使得整体的红外透过率达到90％，硬度达到8GPa，比基底和现有氧化物增透材料性能提高一倍以上。2. Compared with the existing technology, the Gd 2 O 3 film prepared on the ZnS infrared window by the present invention makes the overall infrared transmittance reach 90%, and the hardness reaches 8GPa, which is more anti-reflective than the substrate and the existing oxide The performance of the material is more than doubled.
附图说明Description of drawings
图1为红外透过率图谱；1为实施例一步骤一中所述的衬底材料，2为实施例一步骤四中制备的单面镀有Gd2O3薄膜的衬底材料，3为实施例一步骤五中制备的双面镀有Gd2O3薄膜的衬底材料；Fig. 1 is infrared transmittance spectrum; 1 is the substrate material described in embodiment 1 step 1, and 2 is the single side prepared in embodiment 1 step 4 and is coated with the substrate material of Gd 2 O 3 films, 3 is The double-sided prepared in embodiment 1 step 5 is coated with Gd 2 O The substrate material of the thin film;
图2为硬度测试图谱；1为实施例一步骤一中所述的衬底材料，2为实施例一步骤四中制备的单面镀有Gd2O3薄膜的衬底材料。Figure 2 is a hardness test spectrum; 1 is the substrate material described in step 1 of embodiment 1, and 2 is the substrate material coated with Gd 2 O 3 film on one side prepared in step 4 of embodiment 1.
具体实施方式Detailed ways
具体实施方式一：本实施方式所述的一种长波红外增透保护膜的制备方法是按以下步骤完成的：Embodiment 1: The preparation method of a long-wave infrared antireflection protective film described in this embodiment is completed according to the following steps:
一、靶材和窗口的清洗：1. Cleaning of targets and windows:
在超声功率为100W～300W的条件下，将金属Gd靶材依次置于丙酮、酒精和去离子水中分别清洗10min～20min，然后用氮气吹除表面附着的灰尘，得到洁净靶材；在超声功率为100W～300W的条件下，将ZnS红外窗口材料依次置于丙酮、酒精和去离子水中分别清洗10min～20min，然后用氮气吹除表面附着的灰尘，得到衬底材料；Under the condition of ultrasonic power of 100W-300W, put the metal Gd target in acetone, alcohol and deionized water for 10min-20min respectively, and then use nitrogen to blow off the dust attached to the surface to obtain a clean target; Under the condition of 100W ~ 300W, put the ZnS infrared window material in acetone, alcohol and deionized water for 10min ~ 20min, respectively, and then blow off the dust attached to the surface with nitrogen to obtain the substrate material;
二、镀膜前准备工作：2. Preparatory work before coating:
首先将洁净靶材安装至磁控溅射靶位上，并将衬底材料置于高真空磁控溅射镀膜系统内的加热台中心位置，然后启动真空系统将真空仓内抽成真空，使得真空度为6.5×10-5Pa～5.0×10-4Pa，再启动加热装置，加热衬底材料温度至200℃～700℃；First install the clean target on the magnetron sputtering target position, place the substrate material at the center of the heating table in the high-vacuum magnetron sputtering coating system, and then start the vacuum system to evacuate the vacuum chamber so that Vacuum degree is 6.5×10 -5 Pa～5.0×10 -4 Pa, restart the heating device, and heat the temperature of the substrate material to 200℃～700℃;
三、采用反应溅射的方式制备Gd2O3薄膜：3. Preparation of Gd 2 O 3 thin films by reactive sputtering:
调节氩气气体流量为10sccm～100sccm，调节氧气气体流量为2sccm～10sccm，偏压为-50V～-200V，将真空仓内气体压强调节至0.2Pa～2.0Pa，然后在氩气气体流量为10sccm～100sccm、氧气气体流量为2sccm～10sccm、偏压为-50V～-200V、气体压强为0.2Pa～2.0Pa及衬底材料温度为200℃～700℃的条件下，采用射频电源或高能脉冲电源溅射镀膜；Adjust the flow rate of argon gas to 10sccm~100sccm, adjust the flow rate of oxygen gas to 2sccm~10sccm, the bias voltage to -50V~-200V, adjust the gas pressure in the vacuum chamber to 0.2Pa~2.0Pa, and then adjust the flow rate of argon gas to 10sccm Under the conditions of ～100sccm, oxygen gas flow rate of 2sccm～10sccm, bias voltage of -50V～-200V, gas pressure of 0.2Pa～2.0Pa and substrate material temperature of 200℃～700℃, RF power supply or high-energy pulse power supply is used sputter coating;
当采用射频电源时，溅射功率为50W～200W，先预溅射5min～10min，然后向衬底材料表面镀膜2h～6h；当采用高能脉冲电源时，溅射功率为50W～200W，脉冲频率为10Hz～2000Hz，脉宽20μ～100μ，先预溅射5min～10min，然后向衬底材料表面镀膜2h～6h；When using a radio frequency power supply, the sputtering power is 50W-200W, pre-sputtering for 5min-10min, and then coating the surface of the substrate material for 2h-6h; when using a high-energy pulse power supply, the sputtering power is 50W-200W, pulse frequency 10Hz~2000Hz, pulse width 20μ~100μ, pre-sputter for 5min~10min, and then coat the surface of the substrate material for 2h~6h;
四、结束关机：4. End shutdown:
关闭所有电源并将真空仓内温度降至25℃～70℃，得到单面镀有Gd2O3薄膜的衬底材料；所述的Gd2O3薄膜的厚度为500nm～1500nm；Turn off all power sources and lower the temperature in the vacuum chamber to 25°C-70°C to obtain a substrate material coated with a Gd 2 O 3 film on one side; the thickness of the Gd 2 O 3 film is 500nm-1500nm;
五、双面镀膜：Five, double-sided coating:
将单面镀有Gd2O3薄膜的衬底材料未镀膜的一面按步骤二至步骤四重复进行，得到双面镀有Gd2O3薄膜的衬底材料，即完成一种长波红外增透保护膜的制备方法。Repeat step 2 to step 4 on the uncoated side of the substrate material coated with Gd 2 O 3 film on one side to obtain a substrate material coated with Gd 2 O 3 film on both sides, that is, to complete a long-wave infrared anti-reflection Preparation method of protective film.
本实施方式的有益效果是：1、本实施方式通过在ZnS红外窗口表面镀制具有增透和保护作用的Gd2O3薄膜，提高了红外透过率，提高探测的准确性，并对红外窗口起到保护的作用，提高硬度进而提高其抗沙蚀雨蚀性能。The beneficial effects of this embodiment are: 1. In this embodiment, by coating the surface of the ZnS infrared window with a Gd 2 O 3 film with anti-reflection and protective effects, the infrared transmittance is improved, the accuracy of detection is improved, and the infrared The window plays a protective role, increasing the hardness and thus improving its anti-sand erosion and rain erosion performance.
2、与现有的技术相比，用本发明在ZnS红外窗口上制备的Gd2O3薄膜，使得整体的红外透过率达到90％，硬度达到8GPa，比基底和现有氧化物增透材料性能提高一倍以上。2. Compared with the existing technology, the Gd 2 O 3 film prepared on the ZnS infrared window by the present invention makes the overall infrared transmittance reach 90%, and the hardness reaches 8GPa, which is more anti-reflective than the substrate and the existing oxide The performance of the material is more than doubled.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤一中在超声功率为200W～300W的条件下，将金属Gd靶材依次置于丙酮、酒精和去离子水中分别清洗15min～20min，然后用氮气吹除表面附着的灰尘，得到洁净靶材。其它与具体实施方式一相同。Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that in step 1, under the condition of ultrasonic power of 200W-300W, the metal Gd target is placed in acetone, alcohol and deionized water for 15min to 15min respectively. 20min, and then use nitrogen to blow off the dust attached to the surface to obtain a clean target. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二之一不同的是：步骤一中在超声功率为200W～300W的条件下，将ZnS红外窗口材料依次置于丙酮、酒精和去离子水中分别清洗15min～20min，然后用氮气吹除表面附着的灰尘，得到衬底材料。其它与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in Step 1, the ZnS infrared window material is placed in acetone, alcohol, and deionized water in sequence under the condition of ultrasonic power of 200W to 300W. Wash for 15 min to 20 min respectively, and then blow off the dust attached to the surface with nitrogen to obtain the substrate material. Others are the same as in the first or second embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤二中然后启动真空系统将真空仓内抽成真空，使得真空度为6.5×10-5Pa～5.0×10-4Pa，再启动加热装置，加热衬底材料温度至400℃～700℃。其它与具体实施方式一至三相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that in step 2, the vacuum system is started to evacuate the vacuum chamber so that the degree of vacuum is 6.5×10 -5 Pa to 5.0×10 - 4 Pa, restart the heating device, and heat the substrate material to a temperature of 400°C to 700°C. Others are the same as the specific embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：步骤三中调节氩气气体流量为50sccm～100sccm，调节氧气气体流量为5sccm～10sccm，偏压为-50V～-100V，将真空仓内气体压强调节至1.0Pa～2.0Pa，然后在氩气气体流量为50sccm～100sccm、氧气气体流量为5sccm～10sccm、偏压为-50V～-100V、气体压强为1.0Pa～2.0Pa及衬底材料温度为400℃～700℃的条件下，采用射频电源或高能脉冲电源溅射镀膜。其它与具体实施方式一至四相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that: in step 3, the flow rate of argon gas is adjusted to 50 sccm to 100 sccm, the flow rate of oxygen gas is adjusted to 5 sccm to 10 sccm, and the bias voltage is -50V to -100V , adjust the gas pressure in the vacuum chamber to 1.0Pa ~ 2.0Pa, and then when the argon gas flow rate is 50sccm ~ 100sccm, the oxygen gas flow rate is 5sccm ~ 10sccm, the bias voltage is -50V ~ -100V, and the gas pressure is 1.0Pa ~ 2.0 Under the condition of Pa and substrate material temperature of 400℃～700℃, radio frequency power supply or high energy pulse power supply is used for sputtering coating. Others are the same as the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：步骤三中当采用射频电源时，溅射功率为100W～200W，先预溅射7min～10min，然后向衬底材料表面镀膜4h～6h。其它与具体实施方式一至五相同。Specific Embodiment 6: The difference between this embodiment and one of specific embodiments 1 to 5 is that in step 3, when the radio frequency power supply is used, the sputtering power is 100W-200W, and the sputtering is performed for 7min-10min, and then the sputtering is performed on the substrate material. Surface coating 4h ~ 6h. Others are the same as those in Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：步骤三中当采用高能脉冲电源时，溅射功率为100W～200W，脉冲频率为1000Hz～2000Hz，脉宽50μ～100μ，先预溅射7min～10min，然后向衬底材料表面镀膜4h～6h。其它与具体实施方式一至六相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that: in step 3, when a high-energy pulse power supply is used, the sputtering power is 100W-200W, the pulse frequency is 1000Hz-2000Hz, and the pulse width is 50μ-100μ , first pre-sputtering for 7min ~ 10min, and then coating the surface of the substrate material for 4h ~ 6h. Others are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：步骤四中关闭所有电源并将真空仓内温度降至50℃～70℃，得到单面镀有Gd2O3薄膜的衬底材料。其它与具体实施方式一至七相同。Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that in step 4, all power sources are turned off and the temperature in the vacuum chamber is lowered to 50°C to 70°C to obtain a single-side coated Gd 2 O 3 film the substrate material. Others are the same as those in Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：步骤四中所述的Gd2O3薄膜的厚度为800nm～1500nm。其它与具体实施方式一至八相同。Embodiment 9: This embodiment is different from Embodiment 1 to Embodiment 8 in that: the thickness of the Gd 2 O 3 thin film described in Step 4 is 800nm-1500nm. Others are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：步骤四中所述的Gd2O3薄膜的厚度为500nm～800nm。其它与具体实施方式一至九相同。Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the thickness of the Gd 2 O 3 thin film described in Step 4 is 500nm-800nm. Others are the same as the specific embodiments 1 to 9.
采用以下实施例验证本发明的有益效果：Adopt the following examples to verify the beneficial effects of the present invention:
实施例一：Embodiment one:
本实施例所述的一种长波红外增透保护膜的制备方法是按以下步骤完成的：The preparation method of a kind of long-wave infrared anti-reflection protective film described in this embodiment is completed according to the following steps:
一、靶材和窗口的清洗：1. Cleaning of targets and windows:
在超声功率为150W的条件下，将金属Gd靶材依次置于丙酮、酒精和去离子水中分别清洗15min，然后用氮气吹除表面附着的灰尘，得到洁净靶材；在超声功率为150W的条件下，将ZnS红外窗口材料依次置于丙酮、酒精和去离子水中分别清洗15min，然后用氮气吹除表面附着的灰尘，得到衬底材料；Under the condition of ultrasonic power of 150W, the metal Gd target was cleaned in acetone, alcohol and deionized water for 15 minutes respectively, and then the dust attached to the surface was blown off with nitrogen to obtain a clean target; under the condition of ultrasonic power of 150W Next, the ZnS infrared window material was placed in acetone, alcohol and deionized water for 15 minutes respectively, and then the dust attached to the surface was blown off with nitrogen to obtain the substrate material;
二、镀膜前准备工作：2. Preparatory work before coating:
首先将洁净靶材安装至磁控溅射靶位上，并将衬底材料置于高真空磁控溅射镀膜系统内的加热台中心位置，然后启动真空系统将真空仓内抽成真空，使得真空度为8.0×10-5Pa，再启动加热装置，加热衬底材料温度至400℃；First install the clean target on the magnetron sputtering target position, place the substrate material at the center of the heating table in the high-vacuum magnetron sputtering coating system, and then start the vacuum system to evacuate the vacuum chamber so that The vacuum degree is 8.0×10 -5 Pa, then start the heating device, and heat the temperature of the substrate material to 400°C;
三、采用反应溅射的方式制备Gd2O3薄膜：3. Preparation of Gd 2 O 3 thin films by reactive sputtering:
调节氩气气体流量为50sccm，调节氧气气体流量为3sccm，偏压为-100V，将真空仓内气体压强调节至0.3Pa，然后在氩气气体流量为50sccm、氧气气体流量为3sccm、偏压为-100V、气体压强为0.3Pa及衬底材料温度为400℃的条件下，采用高能脉冲电源溅射镀膜；Adjust the argon gas flow rate to 50 sccm, adjust the oxygen gas flow rate to 3 sccm, and the bias voltage to -100V, adjust the gas pressure in the vacuum chamber to 0.3 Pa, and then adjust the argon gas flow rate to 50 sccm, the oxygen gas flow rate to 3 sccm, and the bias voltage to Under the conditions of -100V, gas pressure of 0.3Pa and substrate material temperature of 400℃, high-energy pulse power supply is used for sputtering coating;
电源采用高能脉冲电源，溅射功率为120W，脉冲频率为800Hz，脉宽30μ，先预溅射10min，然后向衬底材料表面镀膜4.5h；The power supply adopts a high-energy pulse power supply, the sputtering power is 120W, the pulse frequency is 800Hz, and the pulse width is 30μ. First, pre-sputter for 10 minutes, and then coat the surface of the substrate material for 4.5 hours;
四、结束关机：4. End shutdown:
关闭所有电源并将真空仓内温度降至30℃，得到单面镀有Gd2O3薄膜的衬底材料；所述的Gd2O3薄膜的厚度为1300nm；Turn off all power sources and lower the temperature in the vacuum chamber to 30°C to obtain a substrate material coated with a Gd 2 O 3 film on one side; the thickness of the Gd 2 O 3 film is 1300nm;
五、双面镀膜：Five, double-sided coating:
将单面镀有Gd2O3薄膜的衬底材料未镀膜的一面按步骤二至步骤四重复进行，得到双面镀有Gd2O3薄膜的衬底材料，即完成一种长波红外增透保护膜的制备方法。Repeat step 2 to step 4 on the uncoated side of the substrate material coated with Gd 2 O 3 film on one side to obtain a substrate material coated with Gd 2 O 3 film on both sides, that is, to complete a long-wave infrared anti-reflection Preparation method of protective film.
图1为红外透过率图谱；1为实施例一步骤一中所述的衬底材料，2为实施例一步骤四制备的单面镀有Gd2O3薄膜的衬底材料，3为实施例一步骤五制备的双面镀有Gd2O3薄膜的衬底材料；由图可知，单面镀Gd2O3薄膜后红外透过率最高达到82％，双面镀膜后的透过率进一步提高，可达90％。Fig. 1 is infrared transmittance spectrum; 1 is the substrate material described in embodiment one step one, and 2 is the substrate material that the single side of embodiment one step four preparation is coated with Gd 2 O 3 film, 3 is the substrate material of implementation The substrate material coated with Gd 2 O 3 film on both sides prepared in Step 5 of Example 1; it can be seen from the figure that the infrared transmittance after one-side coating of Gd 2 O 3 film reaches a maximum of 82%, and the transmittance after double-side coating Further increase, up to 90%.
图2为硬度测试图谱；1为实施例一步骤一中所述的衬底材料，2为实施例一步骤四制备的单面镀有Gd2O3薄膜的衬底材料。由图可知，硬度较基底提高一倍，达到8GPa，能够起到保护的作用。Figure 2 is a hardness test spectrum; 1 is the substrate material described in step 1 of embodiment 1, and 2 is the substrate material coated with Gd 2 O 3 film on one side prepared in step 4 of embodiment 1. It can be seen from the figure that the hardness is double that of the substrate, reaching 8GPa, which can play a protective role.
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