WO2020192217A1 - Passivating method and passivating apparatus applicable to laser discharge chamber - Google Patents

Passivating method and passivating apparatus applicable to laser discharge chamber Download PDF

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Publication number
WO2020192217A1
WO2020192217A1 PCT/CN2019/129180 CN2019129180W WO2020192217A1 WO 2020192217 A1 WO2020192217 A1 WO 2020192217A1 CN 2019129180 W CN2019129180 W CN 2019129180W WO 2020192217 A1 WO2020192217 A1 WO 2020192217A1
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Prior art keywords
passivation
discharge
gas
discharge chamber
vacuum
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PCT/CN2019/129180
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French (fr)
Chinese (zh)
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沙鹏飞
杨军红
刘广义
熊光亮
贺跃坡
韩晓泉
宋兴亮
陈刚
冯泽斌
丁金滨
刘斌
辛茗
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北京科益虹源光电技术有限公司
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Publication of WO2020192217A1 publication Critical patent/WO2020192217A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/02—Constructional details
    • H01S3/03—Constructional details of gas laser discharge tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/02—Constructional details
    • H01S3/03—Constructional details of gas laser discharge tubes
    • H01S3/036—Means for obtaining or maintaining the desired gas pressure within the tube, e.g. by gettering, replenishing; Means for circulating the gas, e.g. for equalising the pressure within the tube

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  • This application belongs to the technical field of laser discharge cavity passivation, and particularly relates to a passivation method and passivation device suitable for excimer laser discharge cavity.
  • the excimer laser has a short laser wavelength and has no thermal effect on materials, so it has a wide range of applications in the field of industrial processing. Especially in the field of high-end lithography, the excimer laser, which has the characteristics of high repetition frequency, narrow line width and large energy, has become the dominant light source in the field of semiconductor lithography.
  • the mainstream commercial excimer lasers are ArF excimer lasers at 193nm and KrF excimer lasers at 248nm.
  • the working gas of these two kinds of lasers contains a certain proportion of about 0.1% halogen gas F 2.
  • F 2 has very active chemical properties and strong oxidizing properties. Except for perfluorinated compounds, it can interact with almost all organic and inorganic substances. reaction.
  • the inner wall of the discharge chamber and the working gas contacts the excimer laser, the impurities contained in the discharge chamber of a metal material mainly is C, Si and impurities remaining in the gas discharge chamber assembly mainly O 2, H 2 O etc. will react with F 2, resulting in F 2 is consumed.
  • This film serves to convert the metal to corrosive media F 2 are completely separated role in preventing corrosion of metal in contact with medium F 2, so that the metal forming a passivation F substantially stop the reaction with the corrosive medium 2, thereby reducing the F 2 consumption reaches effect.
  • One of the objectives of the present application is to provide a new passivation method suitable for the laser discharge cavity, so as to solve the problem that the discharge cavity is easily polluted and the passivation cost is relatively high caused by the traditional passivation method.
  • the second purpose of the present application is to provide a passivation device that can implement the passivation method.
  • the passivation device has a simple structure, is easy to implement and simple to operate.
  • a passivation method suitable for laser discharge cavity includes:
  • S4 Stop baking after the preliminary passivation is completed, and fill the discharge chamber with working gas to perform discharge passivation.
  • Step S1 includes:
  • step S12 the step of "maintaining the first temperature for 20-24 hours so that the material composing the discharge cavity releases the second impurity gas" also includes: using mass spectrometry The meter monitors the content of each component of the second impurity gas.
  • the technical solution adopted in the embodiment of the present application further includes: the first temperature is 90-110°C.
  • step S11 the step of "evacuating the discharge chamber to exhaust the first impurity gas remaining in the discharge chamber” includes: when the discharge When the vacuum degree of the cavity reaches 0.1-0.5Pa, stop vacuuming; and
  • step S2 the step of "evacuating the discharge chamber so that the impurity gas in the discharge chamber is discharged” includes: stopping the pumping when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa vacuum.
  • Step S3 includes:
  • S31 Fill the discharge cavity with passivation gas for preliminary passivation, and stop charging the passivation gas when the pressure in the discharge cavity reaches a first set value, wherein the passivation gas is Contains F2 with a content of X;
  • step S32 monitoring the remaining content of the F2 by a mass spectrometer, if the remaining content of the F2 is less than 50%X, go to step S33, otherwise continue to monitor the remaining content of the F2;
  • step S33 vacuum the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuum operation, and then return to step S31;
  • the technical solution adopted in the embodiment of the application further includes: the passivation gas is an F2/He mixed gas; and the range of X is 300-500mbar; and/or
  • the range of the first set value is 0.02-0.1 MPa.
  • Step S4 includes:
  • step S42 monitor the energy of the output pulse throughout the entire process, and when the energy is reduced to 50% of the initial output pulse energy, go to step S43, otherwise continue to monitor the energy of the output pulse;
  • step S43 vacuuming the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuuming operation, and then return to step S41;
  • a device suitable for passivating the discharge cavity of a laser is used to implement the above passivation method, and the device includes:
  • a vacuum baking box where the discharge chamber to be passivated is placed in the vacuum baking box;
  • a display and control unit for controlling and displaying the temperature and pressure of the vacuum oven and the discharge chamber
  • the gas supply unit is used to provide passivation gas to the discharge cavity.
  • the device further includes:
  • a gas analyzer for sampling and analyzing the gas in the discharge chamber and the vacuum oven
  • the halogen filter connected to the vacuum pump and the gas analyzer is used to filter and remove halogen in the exhaust gas
  • the pneumatic valves are respectively provided in the gas pipeline connecting the vacuum oven, the vacuum pump, and the gas analyzer, and the discharge chamber, the vacuum pump, and the gas analyzer ,
  • the gas pipeline connected to the gas supply unit is used to control the on-off of the corresponding gas pipeline respectively.
  • the beneficial effects of the embodiments of the present application are: the passivation method suitable for the laser discharge cavity provided by the present application introduces a high-temperature baking discharge cavity and a vacuuming process, which can effectively remove the material in the discharge cavity The impurity gas is released and discharged, which avoids the continuous and bad influence of the discharge cavity material outgassing on the performance of the laser; at the same time, an online monitoring device for the content of the impurity gas and the remaining content of F2 is introduced, which can quantitatively evaluate the passivation process; There is no need to consume Ne gas during the initial passivation process, which reduces the cost of passivation.
  • the provided passivation device that can implement the passivation method has a simple structure, and the equipment used is common experimental equipment, which is easy to implement and simple to operate.
  • Figure 1 is a graph showing the influence of different impurity content on the output energy of the KrF excimer laser.
  • Figure 2 is a flow chart of the passivation method of an embodiment of the present application.
  • Fig. 3 is a schematic structural diagram of a passivation device according to an embodiment of the present application.
  • FIG. 1 shows the influence of different impurity content on the output energy of KrF excimer laser.
  • the figure shows that the impurity concentration of the ppm level can cause a sharp attenuation of the output energy. Therefore, it is very necessary to provide an applicable For the passivation method and device of the laser discharge cavity, please refer to FIG. 2.
  • FIG. 2 is a flow chart of a passivation method provided in an embodiment of the application. The application will be specifically explained below in conjunction with FIG. 2.
  • the passivation method includes the following steps:
  • Step S1 increasing the temperature of the discharge cavity to a first temperature, and maintaining the first temperature to bake the discharge cavity.
  • the introduction of a high-temperature baking material outgassing process in this step can make the discharge chamber material outgas at high temperatures. Too high temperature will damage the sealing performance of the discharge chamber, and too low temperature will reduce the effect of material outgassing.
  • the suitable first temperature is in the range of 90-110°C. In some preferred embodiments, the first temperature is set to 100°C.
  • the discharge can be maintained by any suitable heating device or constant temperature system in the art.
  • the cavity is within the first temperature range to achieve the purpose of baking.
  • this step specifically includes the following steps: step S11, heating the discharge chamber, and vacuuming the discharge chamber to discharge the first impurity gas remaining during assembly of the discharge chamber; step S12 When the temperature of the discharge cavity rises to the first temperature, the first temperature is maintained for 20-24 hours, so that the material constituting the discharge cavity releases the second impurity gas, and then step S2 is performed.
  • step S11 any suitable device in the art can be used to vacuum the discharge chamber, for example, the continuous exhaust of a vacuum pump can achieve a high vacuum in the discharge chamber.
  • the vacuum degree when the discharge chamber When the vacuum degree reaches 0.1-0.5Pa, the vacuum is stopped to ensure that the first impurity gas remaining during the assembly of the discharge chamber is discharged.
  • the vacuum degree is set to 0.1Pa.
  • any suitable gas analysis instrument in the art can be used to monitor the content of each component in the second impurity gas online, such as a mass spectrometer, to obtain the content of each component in the second impurity gas by sampling and analyzing the gas in the discharge chamber. The content of the components can be used to quantitatively determine whether the second impurity gas in the discharge cavity material is effectively released.
  • step S12 lasts for 24 hours, during which sampling is performed 6 times with a sampling period of 4 hours. According to the 6 sets of impurity gas content data obtained by sampling, it is quantitatively determined whether the impurity gases in the discharge cavity material are effectively released. .
  • step S2 the discharge chamber is evacuated so that the impurity gas in the discharge chamber is discharged.
  • the main purpose is to discharge the second impurity gas released by the high-temperature baking of the material constituting the discharge cavity in step S12.
  • the discharge chamber is evacuated through continuous exhaust of the vacuum pump. When the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, the vacuum is stopped. In some preferred embodiments, the set vacuum When the temperature is 0.1Pa, it can ensure that the impurity gas released by the discharge cavity material at high temperature is effectively discharged, thereby greatly reducing the continuous poor performance of the laser caused by the remaining impurities in the discharge cavity such as CO 2 , H 2 O, and Air. influences.
  • the introduction of a mass spectrometer is used for online monitoring of impurity gases, which can quantitatively evaluate the release of impurity gases in the material.
  • step S3 passivation gas is filled into the discharge cavity to perform preliminary passivation on the discharge cavity.
  • This step is to charge a small amount of F 2 into the discharge chamber, and still use high-temperature baking at 90-110°C to accelerate the reaction between F 2 and the discharge chamber material in a high-temperature environment, and form a dense layer of fluorine on the inner wall of the discharge chamber Compound film to achieve preliminary passivation.
  • the selected passivation gas is F 2 /He mixed gas
  • the specific operation steps are as follows: Step S31, fill the discharge cavity with passivation gas for preliminary passivation, when the discharge cavity When the pressure reaches the first set value, stop filling the passivation gas, where the passivation gas contains F 2 with a content of X; step S32, in a high temperature environment, the F 2 reacts with the discharge chamber material and is continued consumed, using a mass spectrometer to monitor the residual content of F 2 can be quantitatively evaluate initial passivation process, if the residual content of F 2 is less than 50% X, into the step S33, the otherwise, continue to monitor the residual content of F 2; step S33, the When the remaining content of F 2 is less than 50%X, the discharge chamber is evacuated to exhaust the remaining passivation gas in the discharge chamber so as to return to step S31 and refill the passivation gas to continue the preliminary passivation process.
  • step S33 it is still selected to stop the vacuum operation when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, preferably the vacuum degree is 0.1 Pa;
  • step S34 the total time of the preliminary passivation process is counted, when the total time reaches 20 -24h, preferably 24h to ensure that the inner wall of the discharge cavity is formed with a more dense and dense fluoride film, and the preliminary passivation process of the discharge cavity can be completed.
  • the discharge chamber is evacuated again to exhaust the remaining passivation gas in the discharge chamber to facilitate the discharge passivation in step S4.
  • the vacuum degree is preferably 0.1Pa.
  • the range of the first set value is 0.02-0.1 MPa. In some preferred embodiments, the first set value is 0.05 MPa. It is determined whether the pressure in the discharge chamber reaches the first set value. A set value is used to judge whether the passivation gas has been sufficient.
  • the passivation gas used is F 2 /He mixed gas, which does not consume Ne gas, which greatly reduces the cost of passivation.
  • the selection of the amount of F 2 charged excessive charging causes waste. If the amount is too small, the process will be repeated too many times and increase the complexity of the operation.
  • the charging amount of a single F 2 is controlled within 300-500 mbar, that is, the range of X in step S31 is 300-500mbar.
  • step S4 the baking is stopped after the preliminary passivation is completed, and the working gas is filled into the discharge chamber to perform discharge passivation. After completion of the bakeout initial passivation and F 2, the discharge chamber of an excimer laser F 2 consumption rate would significantly reduced. Finally, the working gas discharge is replaced for final passivation of the excimer laser discharge cavity and confirmation of the passivation effect. This process is the real working state of the excimer laser. Through the discharge under real working conditions, the fluoride film formed by the material inside the discharge cavity is denser, and the consumption of F 2 by the cavity material is minimized.
  • Step S41 charge working gas into the discharge cavity, start the laser discharge, and output pulses
  • Step S42 monitor the energy of the output pulse throughout the process, when the output pulse energy is reduced to 50% of the initial output pulse energy , Go to step S43, otherwise continue to monitor the energy of the output pulse
  • step S43 vacuum the discharge chamber, exhaust the remaining working gas in the discharge chamber so as to return to step S41 to refill the working gas to continue the discharge passivation
  • step S44 the entire discharge passivation process is recorded by the number of discharge pulses, so the statistics The total number of pulses output by the laser.
  • the discharge passivation is continued; when the total number of pulses is greater than or equal to the second set value, the discharge passivation is stopped, according to some embodiments of the present application ,
  • the range of the second setting value is 150 million-250 million.
  • the output energy of the laser generally decays faster, and the energy will be reduced to About 50% of the initial output energy. At this time, replace the second working gas, continue the discharge passivation, and monitor the output energy throughout the entire process.
  • the energy decay speed will be significantly slower than the first working gas discharge, when the energy decays to 50% of the initial energy After that, replace the working gas for the third time, continue the discharge passivation, monitor the output energy throughout the whole process, the energy decay rate continues to decrease, the laser keeps discharge passivation, until the cumulative discharge passivation pulse number reaches 200 million, you can stop the discharge, and finally complete Passivation process of excimer laser discharge cavity.
  • the device includes: a vacuum baking box in which the discharge chamber to be passivated is placed in the vacuum baking box; a display and control unit It is used to control and display the temperature and pressure of the vacuum oven and the discharge chamber to be passivated; the vacuum pump is used to vacuum the vacuum oven and the discharge chamber to be passivated; the gas supply unit is used to discharge The cavity provides passivation gas; the gas analyzer is used to sample and analyze the gas in the discharge chamber and the vacuum oven; the halogen filter connected to the vacuum pump and the gas analyzer is used to filter and remove the halogen in the exhaust gas to ensure The exhaust gas discharged to the atmosphere meets the emission standards required by environmental safety.
  • FIG. 3 is a schematic structural diagram of a passivation device provided by an embodiment of the application.
  • the passivation device includes a vacuum oven 201, a display and control unit, a vacuum pump 214, an F 2 /He mixed gas 213, The residual gas analyzer 212, the halogen filter 215, and the laser discharge cavity 204 are placed in the vacuum oven 201.
  • the display and control unit includes an oven temperature setting interface 202 and an oven pressure setting interface 203 provided on the vacuum oven 201, and a discharge cavity temperature display interface 205 and a discharge cavity pressure display interface connected to the laser discharge cavity 205 206.
  • the vacuum oven 201 can provide a constant temperature baking temperature range of 20-200°C, temperature fluctuations ⁇ 1°C, and a vacuum range of 1- 0.01MPa.
  • the halogen filter 215 is used to perform F 2 filtering on the exhaust gas.
  • the passivation device also includes five pneumatic valves 207-211, wherein the pneumatic valve 207 is set on the gas pipeline connecting the vacuum oven 201 and the residual gas analyzer 212, and the pneumatic valve 208 is set on the laser discharge On the gas pipeline connecting the cavity 204 and the residual gas analyzer 212, the pneumatic valve 209 is arranged on the gas pipeline connecting the laser discharge cavity 204 and the F 2 /He mixed gas 213, and the pneumatic valve 210 is arranged on the laser discharge cavity 204 and the vacuum pump 214.
  • the pneumatic valve 211 is set on the gas pipeline connecting the vacuum baking box 201 and the vacuum pump 214 on the gas pipeline, and these pneumatic valves are used to control the on and off of the corresponding gas pipeline respectively.
  • the specific operation method of the passivation device is as follows:
  • Discharge cavity baking process Place the laser discharge cavity 204 in the vacuum baking box 201, set the working temperature of the baking box to 100°C through the baking box temperature setting interface 202, open the pneumatic valve 211, and close other pneumatic valves , Turn on the vacuum pump 214 to exhaust the vacuum oven, observe the vacuum oven pressure through the oven pressure setting interface 203, when it reaches the set value of 0.1Mpa, close the pneumatic valve 211 and turn off the vacuum pump 214. Open the pneumatic valve 210, close other pneumatic valves, turn on the vacuum pump 214 to exhaust the laser discharge chamber, observe the discharge chamber pressure through the discharge chamber pressure setting interface 206, when it reaches the set value of 0.1Pa, close the pneumatic valve 210 and turn off the vacuum pump 214.
  • the exhaust of the discharge chamber is completed, and the temperature of the discharge chamber is observed through the discharge chamber temperature setting interface 205.
  • the baking process of the discharge chamber material starts.
  • the process needs to last for 24 hours. It is necessary to monitor the concentration of impurity gases in time intervals, including the inside of the discharge chamber and the vacuum oven, so as to evaluate the outgassing effect. It is recommended
  • the sampling period is 4 hours, that is, 6 sets of impurity gas concentration data are obtained.
  • Open the pneumatic valve 207 close other pneumatic valves, and turn on the residual gas analyzer 212 to sample and analyze the residual gas components inside the vacuum oven 201.
  • F 2 preliminary passivation process After the 24-hour baking process of the discharge chamber is completed, the F 2 preliminary passivation process will be carried out. Open the pneumatic valve 210, close other pneumatic valves, turn on the vacuum pump 214 to exhaust the laser discharge chamber, and pass The discharge chamber pressure setting interface 206 observes the discharge chamber pressure, and when it reaches the set value of 0.1 Pa, closes the pneumatic valve 210 and closes the vacuum pump 214 to complete the exhaust of the discharge chamber.
  • the residual gas analyzer 212 needs to monitor the F 2 content, open the pneumatic valve 208, close other pneumatic valves, and turn on the residual gas analyzer 212 to measure the residual gas composition inside the laser discharge chamber.
  • the passivation device that can implement the passivation method provided above has a simple structure, and the equipment used is common experimental equipment, which is easy to implement and simple to operate.

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Abstract

A passivating method and apparatus applicable to an excimer laser discharge chamber. The passivating method comprises: S1, heating the discharge chamber to a first temperature, and maintaining the first temperature to bake the discharge chamber; S2, vacuumizing the discharge chamber so that foreign gas in the discharge chamber is discharged; S3, filling passivating gas into the discharge chamber to primarily passivate the discharge chamber; and S4, stopping baking after the primary passivation is finished, and filling working gas into the discharge chamber for discharging passivation. The method has the advantages that a passivation process can be quantitatively evaluated, an adverse effect on the performance of the laser caused by degassing of materials of the discharge chamber is avoided, and the passivation costs are reduced. The passivating apparatus comprises: a vacuum baking chamber (201), a display control unit, a vacuum pump (214), a gas supply unit, a residual gas analyzer (212), and a halogen filter (215). The apparatus has the advantages that the structure is simple, the used devices are common experimental devices, implementation is easily performed and the operation is simple.

Description

一种适用于激光器放电腔的钝化方法和钝化装置Passivation method and passivation device suitable for laser discharge cavity 技术领域Technical field
本申请属于激光器放电腔钝化技术领域，特别涉及一种适用于准分子激光器放电腔的钝化方法及钝化装置。This application belongs to the technical field of laser discharge cavity passivation, and particularly relates to a passivation method and passivation device suitable for excimer laser discharge cavity.
背景技术Background technique
准分子激光器的激光波长短,对于材料不产生热效应，因此在工业加工领域有着广泛的应用。尤其在高端光刻领域，同时具备高重频、窄线宽和大能量的特点的准分子激光器，已经成为目前半导体光刻领域占绝对主导地位的光源。The excimer laser has a short laser wavelength and has no thermal effect on materials, so it has a wide range of applications in the field of industrial processing. Especially in the field of high-end lithography, the excimer laser, which has the characteristics of high repetition frequency, narrow line width and large energy, has become the dominant light source in the field of semiconductor lithography.
目前，商用的主流准分子激光器为193nm的ArF准分子激光器和248nm的KrF准分子激光器。这两种激光器的工作气体中均含有一定比例约为0.1％的卤素气体F 2，F 2化学性质十分活泼，具有很强的氧化性，除全氟化合物外，可以与几乎所有有机物和无机物反应。准分子激光器的放电腔内壁与工作气体接触，放电腔金属材料含有的杂质主要是C、Si以及放电腔组装时残存的杂质气体主要是O 2、H 2O等均会与F 2反应，造成F 2消耗，当F 2的含量低于正常含量时，准分子激光器的输出性能就会恶化，甚至造成准分子激光器无法正常工作。因此，为了使准分子激光器能够长时间稳定的工作，在激光器正常运转前，需要对放电腔内部进行充分的钝化处理。钝化的机理可用薄膜理论来解释，即认为钝化是由于放电腔内部金属与F 2作用，在金属表面生成一种非常薄的、致密的、覆盖性能良好的、牢固地吸附在金属表面上的钝化膜，即金属氟化物 薄膜。这层薄膜起着把金属与腐蚀介质F 2完全隔开的作用，防止金属与腐蚀介质F 2接触，从而使金属基本停止与腐蚀介质F 2的反应形成钝态，从而到达降低F 2消耗的作用。 At present, the mainstream commercial excimer lasers are ArF excimer lasers at 193nm and KrF excimer lasers at 248nm. The working gas of these two kinds of lasers contains a certain proportion of about 0.1% halogen gas F 2. F 2 has very active chemical properties and strong oxidizing properties. Except for perfluorinated compounds, it can interact with almost all organic and inorganic substances. reaction. The inner wall of the discharge chamber and the working gas contacts the excimer laser, the impurities contained in the discharge chamber of a metal material mainly is C, Si and impurities remaining in the gas discharge chamber assembly mainly O 2, H 2 O etc. will react with F 2, resulting in F 2 is consumed. When the content of F 2 is lower than the normal content, the output performance of the excimer laser will deteriorate, and even cause the excimer laser to fail to work normally. Therefore, in order to enable the excimer laser to work stably for a long time, it is necessary to fully passivate the inside of the discharge cavity before the laser operates normally. The mechanism of passivation can be explained by film theory, that is, it is believed that the passivation is due to the action of the metal inside the discharge chamber and F 2 to form a very thin, dense, good covering performance, and firmly adsorbed on the metal surface. The passivation film, the metal fluoride film. This film serves to convert the metal to corrosive media F 2 are completely separated role in preventing corrosion of metal in contact with medium F 2, so that the metal forming a passivation F substantially stop the reaction with the corrosive medium 2, thereby reducing the F 2 consumption reaches effect.
目前关于准分子激光器放电腔钝化相关的文章及专利非常少，多数资料也仅仅是关于钝化的定性介绍。而目前商用准分子激光器直接采用工作气体进行放电钝化，需要频繁的更换工作气体，其中F 2及Ne气价格极其昂贵，因此会造成大量的经济损失，并且放电腔排气的真空度仅为约20kPa，无法保证激光器钝化充分及残留的气体杂质完全排除干净。此外一个致命的缺点是放电腔材料会不停的向放电腔内部释放杂质气体，从而持续污染放电腔，造成F 2的消耗，从而影响激光器的输出性能。 At present, there are very few articles and patents related to passivation of excimer laser discharge cavity, and most of the information is only a qualitative introduction to passivation. At present, commercial excimer lasers directly use working gas for discharge passivation, which requires frequent replacement of working gas. Among them, F 2 and Ne gas are extremely expensive, which will cause a lot of economic losses, and the vacuum degree of discharge cavity exhaust is only About 20kPa, it is impossible to ensure that the laser is fully passivated and the remaining gas impurities are completely removed. In addition, a fatal disadvantage is that the discharge cavity material will continuously release impurity gases into the discharge cavity, which will continue to pollute the discharge cavity and cause F 2 consumption, thereby affecting the output performance of the laser.
发明内容Summary of the invention
本申请的目的之一在于提供一种适用于激光器放电腔的新钝化方法，以解决传统的钝化方法所造成的放电腔容易受污染，且钝化成本比较高的问题。One of the objectives of the present application is to provide a new passivation method suitable for the laser discharge cavity, so as to solve the problem that the discharge cavity is easily polluted and the passivation cost is relatively high caused by the traditional passivation method.
本申请的目的之二在于提供一种可以实施该钝化方法的钝化装置，钝化装置结构简单，容易实现且操作简单。The second purpose of the present application is to provide a passivation device that can implement the passivation method. The passivation device has a simple structure, is easy to implement and simple to operate.
为了解决上述技术问题，本申请提供了如下技术方案：In order to solve the above technical problems, this application provides the following technical solutions:
一种适用于激光器放电腔的钝化方法，该方法包括：A passivation method suitable for laser discharge cavity, the method includes:
S1，将所述放电腔的温度升至第一温度，并维持所述第一温度以对所述放电腔进行烘烤；S1, increasing the temperature of the discharge cavity to a first temperature, and maintaining the first temperature to bake the discharge cavity;
S2，对所述放电腔进行抽真空以使得所述放电腔内的杂质气体被排出；S2, evacuating the discharge cavity so that the impurity gas in the discharge cavity is discharged;
S3，向所述放电腔内充入钝化气体以对所述放电腔进行初步钝化；S3: Fill the discharge cavity with a passivation gas to perform preliminary passivation on the discharge cavity;
S4，初步钝化结束后停止烘烤，并向所述放电腔内充入工作气体进行放电钝化。S4: Stop baking after the preliminary passivation is completed, and fill the discharge chamber with working gas to perform discharge passivation.
本申请实施例采取的技术方案还包括：步骤S1包括：The technical solution adopted in the embodiment of the present application further includes: Step S1 includes:
S11，对所述放电腔进行升温，并对所述放电腔进行抽真空以排出所述放电腔内残存的第一杂质气体；S11, raising the temperature of the discharge cavity, and evacuating the discharge cavity to discharge the first impurity gas remaining in the discharge cavity;
S12，当所述放电腔的温度升至第一温度时，维持所述第一温度20-24h，以使得组成所述放电腔的材料释放出第二杂质气体。S12: When the temperature of the discharge cavity rises to a first temperature, maintain the first temperature for 20-24 hours, so that the material composing the discharge cavity releases a second impurity gas.
本申请实施例采取的技术方案还包括：在步骤S12中，“维持所述第一温度20-24h，以使得组成所述放电腔的材料释放出第二杂质气体”的步骤还包括：使用质谱仪监控所述第二杂质气体的各成分含量。The technical solution adopted in the embodiment of the present application further includes: in step S12, the step of "maintaining the first temperature for 20-24 hours so that the material composing the discharge cavity releases the second impurity gas" also includes: using mass spectrometry The meter monitors the content of each component of the second impurity gas.
本申请实施例采取的技术方案还包括：所述第一温度为90-110℃。The technical solution adopted in the embodiment of the present application further includes: the first temperature is 90-110°C.
本申请实施例采取的技术方案还包括：在步骤S11中，所述“并对所述放电腔进行抽真空以排出所述放电腔内残存的第一杂质气体”的步骤包括：当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空；以及The technical solution adopted in the embodiment of the present application further includes: in step S11, the step of "evacuating the discharge chamber to exhaust the first impurity gas remaining in the discharge chamber" includes: when the discharge When the vacuum degree of the cavity reaches 0.1-0.5Pa, stop vacuuming; and
在步骤S2中，所述“对所述放电腔进行抽真空以使得所述放电腔内的杂质气体被排出”的步骤包括：当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空。In step S2, the step of "evacuating the discharge chamber so that the impurity gas in the discharge chamber is discharged" includes: stopping the pumping when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa vacuum.
本申请实施例采取的技术方案还包括：步骤S3包括：The technical solution adopted in the embodiment of the application further includes: Step S3 includes:
S31，向所述放电腔内充入钝化气体进行初步钝化，当所述放电腔内的压强达到第一设定值时停止充入所述钝化气体，其中，所述钝化气体中包含了含量为X的F2；S31: Fill the discharge cavity with passivation gas for preliminary passivation, and stop charging the passivation gas when the pressure in the discharge cavity reaches a first set value, wherein the passivation gas is Contains F2 with a content of X;
S32，通过质谱仪监控所述F2的剩余含量，若所述F2的剩余含量低于50％X时，进入步骤S33，否则继续监控所述F2的剩余含量；S32, monitoring the remaining content of the F2 by a mass spectrometer, if the remaining content of the F2 is less than 50%X, go to step S33, otherwise continue to monitor the remaining content of the F2;
S33，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，再返回至步骤S31；S33, vacuum the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuum operation, and then return to step S31;
S34，统计所述初步钝化过程进行的总时间，当所述总时间达到20-24h时，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空。S34. Count the total time of the preliminary passivation process, when the total time reaches 20-24h, vacuum the discharge chamber, and stop when the vacuum degree of the discharge chamber reaches 0.1-0.5Pa Vacuum.
本申请实施例采取的技术方案还包括：所述钝化气体为F2/He混合气；以及所述X的范围为300-500mbar；和/或The technical solution adopted in the embodiment of the application further includes: the passivation gas is an F2/He mixed gas; and the range of X is 300-500mbar; and/or
所述第一设定值的范围为0.02-0.1MPa。The range of the first set value is 0.02-0.1 MPa.
本申请实施例采取的技术方案还包括：步骤S4包括：The technical solution adopted in the embodiment of the present application further includes: Step S4 includes:
S41，向所述放电腔内充入工作气体，使激光器开始放电，输出脉冲；S41: Fill the discharge cavity with working gas to start the laser discharge and output pulses;
S42，全程监控所述输出脉冲的能量，当所述能量降低至初始输出脉冲能量的50％时，进入步骤S43，否则继续监控所述输出脉冲的能量；S42, monitor the energy of the output pulse throughout the entire process, and when the energy is reduced to 50% of the initial output pulse energy, go to step S43, otherwise continue to monitor the energy of the output pulse;
S43，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，再返回至步骤S41；S43, vacuuming the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuuming operation, and then return to step S41;
S44，统计所述激光器输出的脉冲总数量，当所述脉冲总数量小于第二设定值时，继续放电钝化；当所述脉冲总数量大于或等于第二设定值时，停止放电钝化，其中所述第二设定值的范围为1.5亿-2.5亿。S44. Count the total number of pulses output by the laser, and when the total number of pulses is less than a second set value, continue the discharge passivation; when the total number of pulses is greater than or equal to the second set value, stop the discharge passivation The range of the second set value is 150-250 million.
本申请实施例采取的又一技术方案为：一种适用于钝化激光器放电腔的装置，该钝化装置用来实施上述的钝化方法，所述装置包括：Another technical solution adopted by the embodiments of the present application is: a device suitable for passivating the discharge cavity of a laser. The passivation device is used to implement the above passivation method, and the device includes:
真空烘烤箱，待钝化的放电腔置于所述真空烘烤箱中；A vacuum baking box, where the discharge chamber to be passivated is placed in the vacuum baking box;
显控单元，用于对所述真空烘烤箱和所述放电腔的温度及压力进行控制和显示；A display and control unit for controlling and displaying the temperature and pressure of the vacuum oven and the discharge chamber;
真空泵，用于对所述放电腔和所述真空烘烤箱进行抽真空；A vacuum pump for vacuuming the discharge chamber and the vacuum oven;
气体供给单元，用于向所述放电腔提供钝化气体。The gas supply unit is used to provide passivation gas to the discharge cavity.
优选地，所述装置还包括：Preferably, the device further includes:
气体分析仪，用于对所述放电腔内和所述真空烘烤箱内的气体进行取样分析；A gas analyzer for sampling and analyzing the gas in the discharge chamber and the vacuum oven;
与所述真空泵和所述气体分析仪连接的卤素过滤器，用于过滤除去废气中的卤素；The halogen filter connected to the vacuum pump and the gas analyzer is used to filter and remove halogen in the exhaust gas;
以及若干个气动阀门，所述气动阀门分别设在所述真空烘烤箱与所述真空泵、所述气体分析仪连接的气体管路，以及所述放电腔与所述真空泵、所述气体分析仪、所述气体供给单元连接的气体管路上，用于分别控制相应气体管路的通断。And several pneumatic valves, the pneumatic valves are respectively provided in the gas pipeline connecting the vacuum oven, the vacuum pump, and the gas analyzer, and the discharge chamber, the vacuum pump, and the gas analyzer , The gas pipeline connected to the gas supply unit is used to control the on-off of the corresponding gas pipeline respectively.
相对于现有技术，本申请实施例产生的有益效果在于：本申请提供的适用于激光器放电腔的钝化方法引入了高温烘烤放电腔及抽真空过程，能够有效地将放电腔材料中的杂质气体释放出来并排出去，避免了放电腔材料放气对激光器性能造成的持续的恶劣的影响；同时，引入了对杂质气体的含量和F2剩余含量进行在线监测装置，能够定量评价钝化过程；初步钝化过程中无需消耗Ne气，降低了钝化成本。提供的可以实施该钝化方法的钝化装置结构简单，使用的设备都是常见的实验设备，容易实现且操作简单。Compared with the prior art, the beneficial effects of the embodiments of the present application are: the passivation method suitable for the laser discharge cavity provided by the present application introduces a high-temperature baking discharge cavity and a vacuuming process, which can effectively remove the material in the discharge cavity The impurity gas is released and discharged, which avoids the continuous and bad influence of the discharge cavity material outgassing on the performance of the laser; at the same time, an online monitoring device for the content of the impurity gas and the remaining content of F2 is introduced, which can quantitatively evaluate the passivation process; There is no need to consume Ne gas during the initial passivation process, which reduces the cost of passivation. The provided passivation device that can implement the passivation method has a simple structure, and the equipment used is common experimental equipment, which is easy to implement and simple to operate.
附图说明Description of the drawings
图1是不同杂质含量对KrF准分子激光器输出能量的影响图。Figure 1 is a graph showing the influence of different impurity content on the output energy of the KrF excimer laser.
图2是本申请实施例的钝化方法的流程图。Figure 2 is a flow chart of the passivation method of an embodiment of the present application.
图3是本申请实施例的钝化装置的结构示意图。Fig. 3 is a schematic structural diagram of a passivation device according to an embodiment of the present application.
具体实施方式detailed description
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solutions, and advantages of this application clearer, the following further describes this application in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the application, and not used to limit the application.
为了使本揭示内容的叙述更加详尽与完备，下文针对本申请的实施方式与具体实施例提出了说明性的描述；但这并非实施或运用本申请具体实施例的唯一形式。实施方式中涵盖了多个具体实施例的特征以及用以建构与操作这些具体实施例的方法步骤与其顺序。然而，亦可利用其它具体实施例来达成相同或均等的功能与步骤顺序。In order to make the description of the present disclosure more detailed and complete, the following provides an illustrative description for the implementation and specific examples of the application; this is not the only way to implement or use the specific examples of the application. The implementation manners cover the characteristics of a number of specific embodiments and the method steps and sequences used to construct and operate these specific embodiments. However, other specific embodiments can also be used to achieve the same or equal functions and sequence of steps.
请参阅图1，图1所示为不同杂质含量对KrF准分子激光器输出能量的影响，图中显示ppm量级的杂质浓度就能造成输出能量的急剧衰减，因此，非常有必要提供一种适用于激光器放电腔的钝化方法和装置，请参阅图2，图2为本申请实施例提供的一种钝化方法流程图，下面结合图2对本申请进行具体解释。Please refer to Figure 1. Figure 1 shows the influence of different impurity content on the output energy of KrF excimer laser. The figure shows that the impurity concentration of the ppm level can cause a sharp attenuation of the output energy. Therefore, it is very necessary to provide an applicable For the passivation method and device of the laser discharge cavity, please refer to FIG. 2. FIG. 2 is a flow chart of a passivation method provided in an embodiment of the application. The application will be specifically explained below in conjunction with FIG. 2.
本申请提供了一种适用于激光器放电腔的钝化方法，该钝化方法包括以下步骤：This application provides a passivation method suitable for a laser discharge cavity. The passivation method includes the following steps:
步骤S1，将放电腔的温度升至第一温度，并维持该第一温度以对放电腔进行烘烤。在该步骤中引入高温烘烤材料放气过程，可以使得放电腔材料在高温下放气，温度过高会导致放电腔的密封性能遭到破坏，温度过低会降低材料放气的效果，根据本申请的一些实施例，适宜的第一温度的范围为90-110℃，在一些优选实施例中，设置的第一温度为100℃，可以通过本领域中任何合适的加热设备或恒温系统维持放电腔处于在该第一温度范围内，以实现烘烤目 的。根据本申请的另一些实施例，该步骤具体还包括了以下步骤：步骤S11，对放电腔进行升温，并对该放电腔进行抽真空以排出放电腔组装时残存的第一杂质气体；步骤S12，当放电腔的温度升至第一温度时，维持该第一温度20-24h，以使得组成该放电腔的材料释放出第二杂质气体，然后进入步骤S2。在步骤S11中，可以使用本领域中任何合适的设备来对放电腔进行抽真空，例如通过真空泵的持续排气实现放电腔内的高真空度，在本申请的一些实施例中，当放电腔的真空度达到0.1-0.5Pa时，停止抽真空，即可保证放电腔组装时残存的第一杂质气体被排出，在一些优选实施例中，设定的真空度为0.1Pa。在步骤S12中，可以使用本领域中任何合适的气体分析仪器在线监控第二杂质气体中各成分的含量，例如质谱仪，通过对放电腔中的气体进行取样分析以获得第二杂质气体中各成分的含量，从而定量判断放电腔材料中的第二杂质气体是否均被有效释放出来。在一些优选实施例中，步骤S12持续了24h，期间以采样周期为4h进行了6次采样，根据采样获得的6组杂质气体含量数据定量判断放电腔材料中的杂质气体是否均被有效释放出来。Step S1, increasing the temperature of the discharge cavity to a first temperature, and maintaining the first temperature to bake the discharge cavity. The introduction of a high-temperature baking material outgassing process in this step can make the discharge chamber material outgas at high temperatures. Too high temperature will damage the sealing performance of the discharge chamber, and too low temperature will reduce the effect of material outgassing. In some embodiments of the application, the suitable first temperature is in the range of 90-110°C. In some preferred embodiments, the first temperature is set to 100°C. The discharge can be maintained by any suitable heating device or constant temperature system in the art. The cavity is within the first temperature range to achieve the purpose of baking. According to other embodiments of the present application, this step specifically includes the following steps: step S11, heating the discharge chamber, and vacuuming the discharge chamber to discharge the first impurity gas remaining during assembly of the discharge chamber; step S12 When the temperature of the discharge cavity rises to the first temperature, the first temperature is maintained for 20-24 hours, so that the material constituting the discharge cavity releases the second impurity gas, and then step S2 is performed. In step S11, any suitable device in the art can be used to vacuum the discharge chamber, for example, the continuous exhaust of a vacuum pump can achieve a high vacuum in the discharge chamber. In some embodiments of the present application, when the discharge chamber When the vacuum degree reaches 0.1-0.5Pa, the vacuum is stopped to ensure that the first impurity gas remaining during the assembly of the discharge chamber is discharged. In some preferred embodiments, the vacuum degree is set to 0.1Pa. In step S12, any suitable gas analysis instrument in the art can be used to monitor the content of each component in the second impurity gas online, such as a mass spectrometer, to obtain the content of each component in the second impurity gas by sampling and analyzing the gas in the discharge chamber. The content of the components can be used to quantitatively determine whether the second impurity gas in the discharge cavity material is effectively released. In some preferred embodiments, step S12 lasts for 24 hours, during which sampling is performed 6 times with a sampling period of 4 hours. According to the 6 sets of impurity gas content data obtained by sampling, it is quantitatively determined whether the impurity gases in the discharge cavity material are effectively released. .
步骤S2，对放电腔进行抽真空以使得该放电腔内的杂质气体被排出。在该步骤中，主要是为了将步骤S12中高温烘烤组成放电腔的材料释放出的第二杂质气体排出。根据本申请的一些实施例，通过真空泵的持续排气实现对放电腔进行抽真空，当放电腔的真空度达到0.1-0.5Pa时，停止抽真空，在一些优选实施例中，设定的真空度为0.1Pa，即可保证放电腔材料高温释放的杂质气体被有效的排出，从而大大降低了CO 2、H 2O、Air等残存在放电腔内的杂质对激光器性能造成的持续的恶劣的影响。同时采用引入了质谱仪对杂质气体进行在线监测，能够定量评价材料中的杂质气体释放情况。 In step S2, the discharge chamber is evacuated so that the impurity gas in the discharge chamber is discharged. In this step, the main purpose is to discharge the second impurity gas released by the high-temperature baking of the material constituting the discharge cavity in step S12. According to some embodiments of the present application, the discharge chamber is evacuated through continuous exhaust of the vacuum pump. When the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, the vacuum is stopped. In some preferred embodiments, the set vacuum When the temperature is 0.1Pa, it can ensure that the impurity gas released by the discharge cavity material at high temperature is effectively discharged, thereby greatly reducing the continuous poor performance of the laser caused by the remaining impurities in the discharge cavity such as CO 2 , H 2 O, and Air. influences. At the same time, the introduction of a mass spectrometer is used for online monitoring of impurity gases, which can quantitatively evaluate the release of impurity gases in the material.
步骤S3，向放电腔内充入钝化气体以对放电腔进行初步钝化。该步骤是 为了向放电腔中充入少量的F 2，依然采用90-110℃的高温烘烤，高温环境下加速F 2与放电腔材料的反应，在放电腔的内壁形成一层致密的氟化物薄膜，以实现初步钝化。在本申请的一些实施例中，选择的钝化气体为F 2/He混合气，具体的操作步骤如下：步骤S31，向放电腔内充入钝化气体进行初步钝化，当放电腔内的压强达到第一设定值时停止充入钝化气体，其中,该钝化气体中包含了含量为X的F 2；步骤S32，在高温环境下，F 2与放电腔材料发生反应而被持续消耗掉，使用质谱仪监控F 2的剩余含量，能够定量评价初步钝化过程，若F 2的剩余含量低于50％X时，进入步骤S33，否则继续监控F 2的剩余含量；步骤S33，当F 2的剩余含量低于50％X时，对放电腔进行抽真空，排出放电腔中的剩余钝化气体以便于返回至步骤S31中重新充入钝化气体继续初步钝化过程，在该步骤S33中，仍然选择当放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，优选真空度为0.1Pa；步骤S34，统计该初步钝化过程进行的总时间，当总时间达到20-24h时，优选24h以确保放电腔内壁形成更充分更致密的氟化物薄膜，即可完成对放电腔的初步钝化过程。最后再次对该放电腔进行抽真空，排出放电腔中的剩余钝化气体以便于进入步骤S4中进行放电钝化，该步骤中，仍然选择当放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，优选真空度为0.1Pa。 In step S3, passivation gas is filled into the discharge cavity to perform preliminary passivation on the discharge cavity. This step is to charge a small amount of F 2 into the discharge chamber, and still use high-temperature baking at 90-110°C to accelerate the reaction between F 2 and the discharge chamber material in a high-temperature environment, and form a dense layer of fluorine on the inner wall of the discharge chamber Compound film to achieve preliminary passivation. In some embodiments of the present application, the selected passivation gas is F 2 /He mixed gas, and the specific operation steps are as follows: Step S31, fill the discharge cavity with passivation gas for preliminary passivation, when the discharge cavity When the pressure reaches the first set value, stop filling the passivation gas, where the passivation gas contains F 2 with a content of X; step S32, in a high temperature environment, the F 2 reacts with the discharge chamber material and is continued consumed, using a mass spectrometer to monitor the residual content of F 2 can be quantitatively evaluate initial passivation process, if the residual content of F 2 is less than 50% X, into the step S33, the otherwise, continue to monitor the residual content of F 2; step S33, the When the remaining content of F 2 is less than 50%X, the discharge chamber is evacuated to exhaust the remaining passivation gas in the discharge chamber so as to return to step S31 and refill the passivation gas to continue the preliminary passivation process. In step S33, it is still selected to stop the vacuum operation when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, preferably the vacuum degree is 0.1 Pa; step S34, the total time of the preliminary passivation process is counted, when the total time reaches 20 -24h, preferably 24h to ensure that the inner wall of the discharge cavity is formed with a more dense and dense fluoride film, and the preliminary passivation process of the discharge cavity can be completed. Finally, the discharge chamber is evacuated again to exhaust the remaining passivation gas in the discharge chamber to facilitate the discharge passivation in step S4. In this step, it is still selected to stop when the vacuum degree of the discharge chamber reaches 0.1-0.5Pa For vacuum operation, the vacuum degree is preferably 0.1Pa.
需要说明的是，在步骤S31中，第一设定值的范围为0.02-0.1MPa，在一些优选实施例中该第一设定值为0.05MPa，通过观察放电腔内的压强是否达到该第一设定值来判断是否已经充足钝化气体。在本申请中，使用的钝化气体为F 2/He混合气，没有消耗Ne气，大大降低了钝化成本，而关于F 2的充入量选择，充入量过多造成浪费，充入量过少会导致过程重复次数过多，增加了操作的复杂度，根据本申请的一些实施例，单次F 2的充入量范围控制在 300-500mbar，即步骤S31中的X的范围为300-500mbar。 It should be noted that in step S31, the range of the first set value is 0.02-0.1 MPa. In some preferred embodiments, the first set value is 0.05 MPa. It is determined whether the pressure in the discharge chamber reaches the first set value. A set value is used to judge whether the passivation gas has been sufficient. In this application, the passivation gas used is F 2 /He mixed gas, which does not consume Ne gas, which greatly reduces the cost of passivation. Regarding the selection of the amount of F 2 charged, excessive charging causes waste. If the amount is too small, the process will be repeated too many times and increase the complexity of the operation. According to some embodiments of the present application, the charging amount of a single F 2 is controlled within 300-500 mbar, that is, the range of X in step S31 is 300-500mbar.
步骤S4，初步钝化结束后停止烘烤，并向该放电腔内充入工作气体进行放电钝化。在完成烘烤排气和F 2初步钝化后，准分子激光器的放电腔对F 2的消耗速率就大幅降低了。最后更换工作气体放电进行最终的准分子激光器放电腔钝化及钝化效果确认。该过程是准分子激光器的真实工作状态，通过在真实工况下的放电，使放电腔内部材料形成的氟化物薄膜更加致密，最大程度的降低腔体材料对F 2的消耗。具体的实现步骤如下：步骤S41，向放电腔内充入工作气体，使激光器开始放电，输出脉冲；步骤S42，全程监控输出脉冲的能量，当输出脉冲能量降低至初始输出脉冲能量的50％时，进入步骤S43，否则继续监控所述输出脉冲的能量；步骤S43，对该放电腔进行抽真空，排出放电腔中的剩余工作气体以便于返回至步骤S41中重新充入工作气体继续放电钝化；该步骤中，仍然选择当放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，优选真空度为0.1Pa；步骤S44，整个放电钝化过程以放电脉冲数进行记录，因此统计该激光器输出的脉冲总数量，当脉冲总数量小于第二设定值时，继续放电钝化；当脉冲总数量大于或等于第二设定值时，停止放电钝化，根据本申请的一些实施例，第二设定值的范围为1.5亿-2.5亿，在一些优选实施例中，第一次充入工作气体放电，激光器的输出能量衰减速度一般比较快，两三个小时后能量会降低到初始输出能量的50％左右，此时更换第二次工作气体，继续放电钝化，全程监控输出能量，能量衰减速度会明显比第一次工作气体放电慢，当能量衰减为初始能量的50％后，更换第三次工作气体，继续放电钝化，全程监控输出能量，能量衰减速率继续下降，激光器一直放电钝化，直至累计放电钝化脉冲数达到2亿时，就可以停止放电，最终完成准分子激光器放电腔的钝化过程。 In step S4, the baking is stopped after the preliminary passivation is completed, and the working gas is filled into the discharge chamber to perform discharge passivation. After completion of the bakeout initial passivation and F 2, the discharge chamber of an excimer laser F 2 consumption rate would significantly reduced. Finally, the working gas discharge is replaced for final passivation of the excimer laser discharge cavity and confirmation of the passivation effect. This process is the real working state of the excimer laser. Through the discharge under real working conditions, the fluoride film formed by the material inside the discharge cavity is denser, and the consumption of F 2 by the cavity material is minimized. The specific implementation steps are as follows: Step S41, charge working gas into the discharge cavity, start the laser discharge, and output pulses; Step S42, monitor the energy of the output pulse throughout the process, when the output pulse energy is reduced to 50% of the initial output pulse energy , Go to step S43, otherwise continue to monitor the energy of the output pulse; step S43, vacuum the discharge chamber, exhaust the remaining working gas in the discharge chamber so as to return to step S41 to refill the working gas to continue the discharge passivation In this step, it is still selected to stop the vacuum operation when the vacuum degree of the discharge chamber reaches 0.1-0.5Pa, preferably the vacuum degree is 0.1Pa; step S44, the entire discharge passivation process is recorded by the number of discharge pulses, so the statistics The total number of pulses output by the laser. When the total number of pulses is less than the second set value, the discharge passivation is continued; when the total number of pulses is greater than or equal to the second set value, the discharge passivation is stopped, according to some embodiments of the present application , The range of the second setting value is 150 million-250 million. In some preferred embodiments, when the working gas is charged for the first time to discharge, the output energy of the laser generally decays faster, and the energy will be reduced to About 50% of the initial output energy. At this time, replace the second working gas, continue the discharge passivation, and monitor the output energy throughout the entire process. The energy decay speed will be significantly slower than the first working gas discharge, when the energy decays to 50% of the initial energy After that, replace the working gas for the third time, continue the discharge passivation, monitor the output energy throughout the whole process, the energy decay rate continues to decrease, the laser keeps discharge passivation, until the cumulative discharge passivation pulse number reaches 200 million, you can stop the discharge, and finally complete Passivation process of excimer laser discharge cavity.
经过上述钝化流程的准分子激光器放电腔，在日后的使用过程中，腔体对F 2的消耗速率明显降低，因此工作气体的寿命会大幅提升，极大的提高了准分子激光器输出性能的稳定性并且节约了运行成本。 After the excimer laser discharge cavity undergoes the above passivation process, in the future use process, the consumption rate of F 2 by the cavity is significantly reduced, so the life of the working gas will be greatly increased, which greatly improves the output performance of the excimer laser Stability and saving operating costs.
本申请另一方面还提供了一种可以实施上述钝化方法的钝化装置，该装置包括：真空烘烤箱，待钝化的放电腔置于该真空烘烤箱中；显控单元，用于对真空烘烤箱和待钝化的放电腔的温度及压力进行控制和显示；真空泵，用于对真空烘烤箱和待钝化的放电腔进行抽真空；气体供给单元，用于向放电腔提供钝化气体；气体分析仪，用于对放电腔内和真空烘烤箱内的气体进行取样分析；与真空泵和气体分析仪连接的卤素过滤器，用于过滤除去废气中的卤素，保证排放到大气的废气达到环境安全要求的排放标准。Another aspect of the present application also provides a passivation device that can implement the above passivation method. The device includes: a vacuum baking box in which the discharge chamber to be passivated is placed in the vacuum baking box; a display and control unit It is used to control and display the temperature and pressure of the vacuum oven and the discharge chamber to be passivated; the vacuum pump is used to vacuum the vacuum oven and the discharge chamber to be passivated; the gas supply unit is used to discharge The cavity provides passivation gas; the gas analyzer is used to sample and analyze the gas in the discharge chamber and the vacuum oven; the halogen filter connected to the vacuum pump and the gas analyzer is used to filter and remove the halogen in the exhaust gas to ensure The exhaust gas discharged to the atmosphere meets the emission standards required by environmental safety.
请参阅图3所示，图3为本申请实施例提供的一种钝化装置结构示意图，该钝化装置包括真空烘烤箱201、显控单元、真空泵214、F 2/He混合气213、残气分析仪212和卤素过滤器215，激光器放电腔204置于该真空烘烤箱201中。其中，显控单元包括设于该真空烘烤箱201上的烤箱温度设定界面202和烤箱压力设定界面203、以及与激光器放电腔205连接的放电腔温度显示界面205和放电腔压力显示界面206，通过烤箱温度设定界面202设定所需要的烘烤温度，通过烤箱压力设定界面203设定烤箱所需要的真空度，通过放电腔温度显示界面205观察放电腔内的温度，通过放电腔压力显示界面206观察放电腔内的压力，在本实施例中，该真空烘烤箱201可提供的恒温烘烤温度范围为20-200℃、温度波动≤±1℃、真空范围为1-0.01MPa。在该实施例中，卤素过滤器215用于对废气进行F 2过滤。在该实施例中，该钝化装置还包括5个气动阀门207-211，其中气动阀门207设置在真空烘烤箱201与残气分析仪212连接的气体管路上，气动阀门208设置在激光器放电腔204与残气分析仪212 连接的气体管路上，气动阀门209设置在激光器放电腔204与F 2/He混合气213连接的气体管路上，气动阀门210设置在激光器放电腔204与真空泵214连接的气体管路上，气动阀门211设置在真空烘烤箱201与真空泵214连接的气体管路上，这些气动阀门用于分别控制相应气体管路的通断。该钝化装置的具体操作方法如下： Please refer to FIG. 3, which is a schematic structural diagram of a passivation device provided by an embodiment of the application. The passivation device includes a vacuum oven 201, a display and control unit, a vacuum pump 214, an F 2 /He mixed gas 213, The residual gas analyzer 212, the halogen filter 215, and the laser discharge cavity 204 are placed in the vacuum oven 201. The display and control unit includes an oven temperature setting interface 202 and an oven pressure setting interface 203 provided on the vacuum oven 201, and a discharge cavity temperature display interface 205 and a discharge cavity pressure display interface connected to the laser discharge cavity 205 206. Set the required baking temperature through the oven temperature setting interface 202, set the vacuum required by the oven through the oven pressure setting interface 203, observe the temperature in the discharge cavity through the discharge cavity temperature display interface 205, and pass the discharge The cavity pressure display interface 206 observes the pressure in the discharge cavity. In this embodiment, the vacuum oven 201 can provide a constant temperature baking temperature range of 20-200°C, temperature fluctuations ≤±1°C, and a vacuum range of 1- 0.01MPa. In this embodiment, the halogen filter 215 is used to perform F 2 filtering on the exhaust gas. In this embodiment, the passivation device also includes five pneumatic valves 207-211, wherein the pneumatic valve 207 is set on the gas pipeline connecting the vacuum oven 201 and the residual gas analyzer 212, and the pneumatic valve 208 is set on the laser discharge On the gas pipeline connecting the cavity 204 and the residual gas analyzer 212, the pneumatic valve 209 is arranged on the gas pipeline connecting the laser discharge cavity 204 and the F 2 /He mixed gas 213, and the pneumatic valve 210 is arranged on the laser discharge cavity 204 and the vacuum pump 214. The pneumatic valve 211 is set on the gas pipeline connecting the vacuum baking box 201 and the vacuum pump 214 on the gas pipeline, and these pneumatic valves are used to control the on and off of the corresponding gas pipeline respectively. The specific operation method of the passivation device is as follows:
放电腔烘烤过程：将激光器放电腔204放置于真空烘烤箱201中，通过烘烤箱温度设定界面202设定烘烤箱的工作温度为100℃，打开气动阀211，关闭其它气动阀，开启真空泵214对真空烘烤箱进行排气，通过烘烤箱压力设定界面203观察真空烤箱压力，当达到设定值0.1Mpa时，关闭气动阀211，关闭真空泵214。打开气动阀210，关闭其它气动阀，开启真空泵214对激光器放电腔进行排气，通过放电腔压力设定界面206观察放电腔压力，当达到设定值0.1Pa时，关闭气动阀210，关闭真空泵214，完成对放电腔的排气，通过放电腔温度设定界面205观察放电腔温度。此时即开始了放电腔材料的烘烤过程，该过程需要持续24小时，需要分时段的监控杂质气体的浓度，包括放电腔内部和真空烘烤箱内部，从而对放气效果进行评估，建议的采样周期为4小时，即获得6组杂质气体浓度数据。打开气动阀207，关闭其它气动阀，打开残气分析仪212，即可对真空烘烤箱201内部的残气成分进行取样分析。打开气动阀208，关闭其它气动阀，打开残气分析仪212，即可对激光器放电腔内部的残气成分进行取样分析。Discharge cavity baking process: Place the laser discharge cavity 204 in the vacuum baking box 201, set the working temperature of the baking box to 100℃ through the baking box temperature setting interface 202, open the pneumatic valve 211, and close other pneumatic valves , Turn on the vacuum pump 214 to exhaust the vacuum oven, observe the vacuum oven pressure through the oven pressure setting interface 203, when it reaches the set value of 0.1Mpa, close the pneumatic valve 211 and turn off the vacuum pump 214. Open the pneumatic valve 210, close other pneumatic valves, turn on the vacuum pump 214 to exhaust the laser discharge chamber, observe the discharge chamber pressure through the discharge chamber pressure setting interface 206, when it reaches the set value of 0.1Pa, close the pneumatic valve 210 and turn off the vacuum pump 214. The exhaust of the discharge chamber is completed, and the temperature of the discharge chamber is observed through the discharge chamber temperature setting interface 205. At this time, the baking process of the discharge chamber material starts. The process needs to last for 24 hours. It is necessary to monitor the concentration of impurity gases in time intervals, including the inside of the discharge chamber and the vacuum oven, so as to evaluate the outgassing effect. It is recommended The sampling period is 4 hours, that is, 6 sets of impurity gas concentration data are obtained. Open the pneumatic valve 207, close other pneumatic valves, and turn on the residual gas analyzer 212 to sample and analyze the residual gas components inside the vacuum oven 201. Open the pneumatic valve 208, close other pneumatic valves, and open the residual gas analyzer 212 to sample and analyze the residual gas components inside the laser discharge cavity.
F 2初步钝化过程：完成24小时的放电腔烘烤过程后，紧接着开展F 2初步钝化过程，打开气动阀210，关闭其它气动阀，开启真空泵214对激光器放电腔进行排气，通过放电腔压力设定界面206观察放电腔压力，当达到设定值0.1Pa时，关闭气动阀210，关闭真空泵214，完成对放电腔的排气。打开气动 阀209，关闭其它气动阀，向放电腔内充入钝化气体F 2/He,通过放电腔压力设定界面206观察放电腔压力，当达到设定值0.05MPa时，关闭气动阀209，完成对放电腔的充气。此时即开始放电腔的初步F 2钝化。该过程F 2会被持续消耗，需要通过残气分析仪212监控F 2含量，打开气动阀208，关闭其它气动阀，打开残气分析仪212，即可对激光器放电腔内部的残气成分进行取样分析F 2的含量，当含量低于初始含量的50％时，通过真空泵进行排气并重新充入新的F 2/He继续进行F 2初步钝化，随着该过程的进行，F 2的消耗速度会逐渐降低，当持续24小时后，即可完成放电腔的F 2烘烤的初步钝化过程。 F 2 preliminary passivation process: After the 24-hour baking process of the discharge chamber is completed, the F 2 preliminary passivation process will be carried out. Open the pneumatic valve 210, close other pneumatic valves, turn on the vacuum pump 214 to exhaust the laser discharge chamber, and pass The discharge chamber pressure setting interface 206 observes the discharge chamber pressure, and when it reaches the set value of 0.1 Pa, closes the pneumatic valve 210 and closes the vacuum pump 214 to complete the exhaust of the discharge chamber. Open the pneumatic valve 209, close other pneumatic valves, fill the discharge chamber with passivation gas F 2 /He, observe the discharge chamber pressure through the discharge chamber pressure setting interface 206, and close the pneumatic valve 209 when it reaches the set value of 0.05 MPa , Complete the charging of the discharge chamber. At this point, the preliminary F 2 passivation of the discharge cavity begins. In this process, F 2 will be continuously consumed. The residual gas analyzer 212 needs to monitor the F 2 content, open the pneumatic valve 208, close other pneumatic valves, and turn on the residual gas analyzer 212 to measure the residual gas composition inside the laser discharge chamber. Sampling and analyzing the content of F 2 , when the content is less than 50% of the initial content, exhaust through a vacuum pump and refill with new F 2 /He to continue the initial passivation of F 2. As the process proceeds, F 2 The consumption rate will gradually decrease. When it lasts for 24 hours, the initial passivation process of the F 2 baking of the discharge chamber can be completed.
上述提供的可以实施该钝化方法的钝化装置结构简单，使用的设备都是常见的实验设备，容易实现且操作简单。The passivation device that can implement the passivation method provided above has a simple structure, and the equipment used is common experimental equipment, which is easy to implement and simple to operate.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本申请。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use this application. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined in this document can be implemented in other embodiments without departing from the spirit or scope of the application. Therefore, this application will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (10)

  1. 一种适用于激光器放电腔的钝化方法，其特征在于，包括以下步骤：A passivation method suitable for laser discharge cavity, characterized in that it comprises the following steps:
    S1，将所述放电腔的温度升至第一温度，并维持所述第一温度以对所述放电腔进行烘烤；S1, increasing the temperature of the discharge cavity to a first temperature, and maintaining the first temperature to bake the discharge cavity;
    S2，对所述放电腔进行抽真空以使得所述放电腔内的杂质气体被排出；S2, evacuating the discharge cavity so that the impurity gas in the discharge cavity is discharged;
    S3，向所述放电腔内充入钝化气体以对所述放电腔进行初步钝化；S3: Fill the discharge cavity with a passivation gas to perform preliminary passivation on the discharge cavity;
    S4，初步钝化结束后停止烘烤，并向所述放电腔内充入工作气体进行放电钝化。S4: Stop baking after the preliminary passivation is completed, and fill the discharge chamber with working gas to perform discharge passivation.
  2. 如权利要求1所述的钝化方法，其特征在于，步骤S1包括：The passivation method according to claim 1, wherein step S1 comprises:
    S11，对所述放电腔进行升温，并对所述放电腔进行抽真空以排出所述放电腔内残存的第一杂质气体；S11, raising the temperature of the discharge cavity, and evacuating the discharge cavity to discharge the first impurity gas remaining in the discharge cavity;
    S12，当所述放电腔的温度升至第一温度时，维持所述第一温度20-24h，以使得组成所述放电腔的材料释放出第二杂质气体。S12: When the temperature of the discharge cavity rises to a first temperature, maintain the first temperature for 20-24 hours, so that the material composing the discharge cavity releases a second impurity gas.
  3. 如权利要求2所述的钝化方法，其特征在于，在步骤S12中，“维持所述第一温度20-24h，以使得组成所述放电腔的材料释放出第二杂质气体”的步骤还包括：使用质谱仪监控所述第二杂质气体的各成分含量。The passivation method according to claim 2, wherein in step S12, the step of "maintaining the first temperature for 20-24 hours so that the material composing the discharge cavity releases the second impurity gas" is also It includes: using a mass spectrometer to monitor the content of each component of the second impurity gas.
  4. 如权利要求1-3中任一项所述的钝化方法，其特征在于，所述第一温度为90-110℃。The passivation method according to any one of claims 1-3, wherein the first temperature is 90-110°C.
  5. 如权利要求2所述的钝化方法，其特征在于，在步骤S11中，所述“并对所述放电腔进行抽真空以排出所述放电腔内残存的第一杂质气体”的步骤包括：当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空；以及The passivation method according to claim 2, wherein in step S11, the step of "evacuating the discharge chamber to exhaust the first impurity gas remaining in the discharge chamber" comprises: When the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop vacuuming; and
    在步骤S2中，所述“对所述放电腔进行抽真空以使得所述放电腔内的杂质 气体被排出”的步骤包括：当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空。In step S2, the step of "evacuating the discharge chamber so that the impurity gas in the discharge chamber is discharged" includes: stopping the pumping when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa vacuum.
  6. 如权利要求1所述的钝化方法，其特征在于，步骤S3包括：The passivation method of claim 1, wherein step S3 comprises:
    S31，向所述放电腔内充入钝化气体进行初步钝化，当所述放电腔内的压强达到第一设定值时停止充入所述钝化气体，其中，所述钝化气体中包含了含量为X的F 2； S31: Fill the discharge cavity with passivation gas for preliminary passivation, and stop charging the passivation gas when the pressure in the discharge cavity reaches a first set value, wherein the passivation gas is Contains F 2 with a content of X;
    S32，通过质谱仪监控所述F 2的剩余含量，若所述F 2的剩余含量低于50％X时，进入步骤S33，否则继续监控所述F 2的剩余含量； S32, monitoring the remaining content of the F 2 by a mass spectrometer, if the remaining content of the F 2 is less than 50% X, go to step S33, otherwise continue to monitor the remaining content of the F 2 ;
    S33，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，再返回至步骤S31；S33, vacuum the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuum operation, and then return to step S31;
    S34，统计所述初步钝化过程进行的总时间，当所述总时间达到20-24h时，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空。S34. Count the total time of the preliminary passivation process, when the total time reaches 20-24h, vacuum the discharge chamber, and stop when the vacuum degree of the discharge chamber reaches 0.1-0.5Pa Vacuum.
  7. 如权利要求6所述的钝化方法，其特征在于，所述钝化气体为F 2/He混合气；以及所述X的范围为300-500mbar；和/或 The passivation method of claim 6, wherein the passivation gas is a mixture of F 2 /He; and the range of X is 300-500 mbar; and/or
    所述第一设定值的范围为0.02-0.1MPa。The range of the first set value is 0.02-0.1 MPa.
  8. 如权利要求1所述的钝化方法，其特征在于，步骤S4包括：The passivation method according to claim 1, wherein step S4 comprises:
    S41，向所述放电腔内充入工作气体，使激光器开始放电，输出脉冲；S41: Fill the discharge cavity with working gas to start the laser discharge and output pulses;
    S42，全程监控所述输出脉冲的能量，当所述能量降低至初始输出脉冲能量的50％时，进入步骤S43，否则继续监控所述输出脉冲的能量；S42, monitor the energy of the output pulse throughout the entire process, and when the energy is reduced to 50% of the initial output pulse energy, go to step S43, otherwise continue to monitor the energy of the output pulse;
    S43，对所述放电腔进行抽真空，当所述放电腔的真空度达到0.1-0.5Pa时，停止抽真空操作，再返回至步骤S41；S43, vacuuming the discharge chamber, and when the vacuum degree of the discharge chamber reaches 0.1-0.5 Pa, stop the vacuuming operation, and then return to step S41;
    S44，统计所述激光器输出的脉冲总数量，当所述脉冲总数量小于第二设定值时，继续放电钝化；当所述脉冲总数量大于或等于第二设定值时，停止放电 钝化，其中所述第二设定值的范围为1.5亿-2.5亿。S44. Count the total number of pulses output by the laser, and when the total number of pulses is less than a second set value, continue the discharge passivation; when the total number of pulses is greater than or equal to the second set value, stop the discharge passivation The range of the second set value is 150-250 million.
  9. 一种适用于激光器放电腔的钝化装置，其特征在于，该钝化装置用来实施权利要求1-8中任一项所述的钝化方法，所述装置包括：A passivation device suitable for a laser discharge cavity, characterized in that the passivation device is used to implement the passivation method of any one of claims 1-8, and the device comprises:
    真空烘烤箱，待钝化的放电腔置于所述真空烘烤箱中；A vacuum baking box, where the discharge chamber to be passivated is placed in the vacuum baking box;
    显控单元，用于对所述真空烘烤箱和所述放电腔的温度及压力进行控制和显示；A display and control unit for controlling and displaying the temperature and pressure of the vacuum oven and the discharge chamber;
    真空泵，用于对所述放电腔和所述真空烘烤箱进行抽真空；A vacuum pump for vacuuming the discharge chamber and the vacuum oven;
    气体供给单元，用于向所述放电腔提供钝化气体。The gas supply unit is used to provide passivation gas to the discharge cavity.
  10. 如权利要求9所述的装置，其特征在于，所述装置还包括：The device of claim 9, wherein the device further comprises:
    气体分析仪，用于对所述放电腔内和所述真空烘烤箱内的气体进行取样分析；A gas analyzer for sampling and analyzing the gas in the discharge chamber and the vacuum oven;
    与所述真空泵和所述气体分析仪连接的卤素过滤器，用于过滤除去废气中的卤素；The halogen filter connected to the vacuum pump and the gas analyzer is used to filter and remove halogen in the exhaust gas;
    以及若干个气动阀门，所述气动阀门分别设在所述真空烘烤箱与所述真空泵、所述气体分析仪连接的气体管路，以及所述放电腔与所述真空泵、所述气体分析仪、所述气体供给单元连接的气体管路上，用于分别控制相应气体管路的通断。And several pneumatic valves, the pneumatic valves are respectively provided in the gas pipeline connecting the vacuum oven, the vacuum pump, and the gas analyzer, and the discharge chamber, the vacuum pump, and the gas analyzer , The gas pipeline connected to the gas supply unit is used to control the on-off of the corresponding gas pipeline respectively.
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