阅读说明：本技术 一种高透过率条纹变像管加速栅网制备方法 (Preparation method of high-transmittance stripe image converter tube accelerating grid mesh ) 是由 张昆林 谭何盛 杨文波 靳英坤 邓华兵 张世超 冯云祥 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种高透过率条纹变像管加速栅网制备方法。该制备方法包括的步骤有：1)原材料准备、2)镀膜、3)光刻、4)铬的湿法腐蚀、5)铜的湿法腐蚀、6)去铬膜、去胶和7)电镀。本发明的制备方法利用铬与铜的表面粘接性好的特点,具体采用在铜箔表面镀上一层铬、光刻并腐蚀铬做出铬金属掩膜版图案的方法,用金属掩膜图案替代光刻胶掩膜图案,用铬来做铜箔的掩膜,再腐蚀铜箔做出栅网。另外,传统的栅网开口比都在49％以下,本发明设计的栅网开口比在53.8％～68.2％之间,制备出的栅网具有更高的电子透过率。(The invention discloses a preparation method of a high-transmittance stripe image converter tube accelerating grid mesh. The preparation method comprises the following steps: 1) raw material preparation, 2) plating, 3) photoetching, 4) wet etching of chromium, 5) wet etching of copper, 6) chromium removal, photoresist removal and 7) electroplating. The preparation method of the invention utilizes the characteristic of good surface adhesion of chromium and copper, and particularly adopts a method of plating a layer of chromium on the surface of the copper foil, photoetching and corroding the chromium to make a chromium metal mask pattern, wherein the metal mask pattern is used for replacing a photoresist mask pattern, the chromium is used for making a mask of the copper foil, and then the copper foil is corroded to make a grid mesh. In addition, the opening ratio of the traditional grid is below 49%, the opening ratio of the grid designed by the invention is between 53.8% and 68.2%, and the prepared grid has higher electron transmittance.)

1. A preparation method of a high-transmittance stripe image converter tube accelerating grid is characterized by comprising the following steps:

1) preparing raw materials, namely photoetching a mask plate, copper foil with the thickness of 3-6 mu m, and flatly adhering the copper foil on a glass substrate by using photoresist and a cylindrical rolling tool;

2) plating a film, including evaporating chrome on the surface of the copper foil and performing plasma cleaning on the surface of the chrome;

3) photoetching, including coating a layer of tackifier primer solution on the chromium surface, then uniformly coating a layer of photoresist, prebaking, photoetching, developing and hardening;

4) wet etching of chromium;

5) wet etching of copper;

6) removing the chromium film and the photoresist;

7) electroplating a layer of nickel on the surface of the copper grid.

2. The method for preparing the accelerating grid of the high-transmittance streak image converter tube according to claim 1, wherein the specific steps of the step 1) are as follows:

1.1) designing and manufacturing a photoetching mask plate corresponding to the pattern when the opening ratio of the grid is 53.8% -68.2%, wherein the grid is formed by periodically repeating hollow grids and grid bars, the size A of each hollow grid is 19-22 mu m, and the size B of each grid bar is 4-8 mu m;

1.2) cutting a double-sided polished electrolytic copper foil with the thickness of 3-6 microns well by laser cutting, pickling with a solution prepared from 50ml of glacial acetic acid, 150g of sodium chloride, 25ml of hydrochloric acid and 500ml of deionized water, and then ultrasonically cleaning and drying with deionized water;

1.3) applying the copper foil to the glass substrate by means of photoresist and a cylinder rolling tool, and is named C.

3. The method for preparing the high-transmittance streak image converter tube accelerating grid according to claim 1 or 2, characterized in that the specific steps of the step 2) are as follows:

2.1) firstly carrying out plasma brushing on the surface of the copper foil on the C for 5 minutes by using a plasma brushing machine, then horizontally fixing the C and a special clamp in a film plating machine in a matching way, and evaporating a layer on the surface of the copper foil on the CChromium (iv) is designated as D;

2.2) taking the D out of the film coating machine, and carrying out plasma brushing on the surface of the chromium film layer on the D for 5 minutes by using a plasma brushing machine.

4. The method for preparing the accelerating grid of the high-transmittance fringe image converter tube according to claim 3, wherein the step 3) comprises the following steps:

3.1) placing D on a spin coater, uniformly coating a layer of tackifier primer solution HMDS on the chromium surface of D, then running for 3 seconds at 500 revolutions per second, and then running for 30 seconds at 5000 revolutions per second for spin coating with a layer of photoresist AZ6130, which is called E;

3.2) prebaking: placing the E on a hot plate, baking the E for 2 minutes at 100 ℃, and transferring the E to a photoetching machine;

3.3) photoetching: the exposure time of the photoetching machine is set to be 3.9s, and the exposure intensity is set to be 30mW/cm²Exposing the photoresist on the surface E;

3.4) developing: placing the exposed E in a prepared ZX238 developing solution for developing for 25s, cleaning with deionized water, and blow-drying with nitrogen, wherein the F is called;

3.5) hardening: and F is placed on a hot plate, baked for 3 minutes at 120 ℃ and subjected to photoresist hardening treatment.

5. The method for preparing the accelerating grid of the high-transmittance fringe image converter tube as claimed in claim 4, wherein the specific step of the step 4) is:

4.1) preparing cerium ammonium nitrate corrosive liquid, placing F into the corrosive liquid, and corroding for 90 seconds under the condition of water bath at 30 ℃;

4.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun.

6. The method for preparing the accelerating grid of the high-transmittance fringe image converter tube as claimed in claim 5, wherein the step 5) comprises the following steps:

5.1) preparing a copper corrosive liquid, placing F into the copper corrosive liquid, and corroding for 120 seconds under the condition of water bath at 40 ℃;

and 5.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun to obtain the product G.

7. The method for preparing the accelerating grid of the high-transmittance fringe image converter tube as claimed in claim 6, wherein the step 6) comprises the following steps:

6.1) placing the G on a rotating table, uniformly spraying an acetone solution on the surface of the G, and removing the photoresist on the G, namely H;

6.2) putting H into cerium ammonium nitrate corrosive liquid, corroding for 10 minutes in a water bath at the temperature of 30 ℃, and taking out the H after chromium is completely corroded to be I;

6.3) cleaning the I with deionized water, and drying with a nitrogen gun;

6.4) soaking the I in an acetone solution to dissolve the photoresist between the copper foil and the glass substrate;

6.5) removing the copper grid from the glass substrate, and carrying out cleaning and drying treatment.

8. The method for preparing the accelerating grid of the high-transmittance fringe image converter tube as claimed in claim 7, wherein the step 7) comprises the following steps:

7.1) electroplating a layer of nickel on the surface of the copper grid mesh for anti-oxidation protection, and finishing the accelerated grid mesh manufacturing.

Technical Field

The invention relates to the technical field of photoelectric devices, in particular to a method for preparing an accelerating grid mesh of a high-transmittance stripe image converter tube.

Background

The grid mesh is an important component of electronic and optical instruments such as a stripe image converter tube and the like, and has the characteristics of good electric conductivity, good heat conductivity, easy processing and easy degassing.

The grid mesh is arranged behind the photocathode of the fringe image converter and is away from the photocathode by a certain distance, so that the acceleration field intensity of photoelectrons can be greatly improved, the time and space broadening caused by initial energy dispersion and space charge effect of electrons is reduced, and the time resolution of the fringe image converter is improved to ps magnitude. The accelerating grid can form a strong accelerating electric field or a grid shielding field, and is widely applied to electronic optical instruments such as stripe cameras, framing cameras, electron diffractometers, ion energy analyzers, scanning electron microscopes, ion accelerators and the like.

In a diagnostic instrument with high time and space resolution, such as a fringe imager, the grid bars are usually several to ten and several microns, and the precision requirement is very high. In order to increase the number of signal electrons and improve the signal-to-noise ratio of the fringe image converter, the area of the mesh of the grid needs to be enlarged and the aperture ratio needs to be increased. The accelerated grid can be manufactured by using a method of etching the copper foil after photoetching, but the method of etching after photoetching cannot manufacture a complete accelerated grid because the adhesion between the copper foil and the photoresist is not strong.

The traditional aperture ratio of the grid is below 49%, and the industry needs to invent a preparation method, so that the prepared grid has larger aperture ratio and higher electron transmittance. The requirement of a high-transmittance stripe image converter is met.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for preparing a high-transmittance stripe image converter tube acceleration grid, the opening ratio of the grid prepared by the method is between 53.8% and 68.2%, and the prepared grid has higher electron transmittance.

The technical scheme of the invention is as follows:

a preparation method of a high-transmittance stripe image converter tube accelerating grid comprises the following steps:

1) preparing raw materials, namely photoetching a mask plate, copper foil with the thickness of 3-6 mu m, and flatly adhering the copper foil on a glass substrate by using photoresist and a cylindrical rolling tool;

2) plating a film, including evaporating chrome on the surface of the copper foil and performing plasma cleaning on the surface of the chrome;

3) photoetching, including coating a layer of tackifier primer solution on the chromium surface, then uniformly coating a layer of photoresist, prebaking, photoetching, developing and hardening;

4) wet etching of chromium;

5) wet etching of copper;

6) removing the chromium film and the photoresist;

7) electroplating a layer of nickel on the surface of the copper grid.

The specific steps of the step 1) are as follows:

1.1) designing and manufacturing a photoetching mask plate corresponding to patterns when the opening ratio of a grid is 53.8-68.2%, wherein the grid is formed by periodically repeating hollow grids A and grid bars B, the size range of the hollow grids A is 19-22 mu m, and the size range of the grid bars B is 4-8 mu m;

1.2) cutting a double-sided polished electrolytic copper foil with the thickness of 3-6 microns well by laser cutting, pickling with a solution prepared from 50ml of glacial acetic acid, 150g of sodium chloride, 25ml of hydrochloric acid and 500ml of deionized water, and then ultrasonically cleaning and drying with deionized water;

1.3) applying the copper foil to the glass substrate by means of photoresist and a cylinder rolling tool, and is named C.

The specific steps of the step 2) are as follows:

2.1) firstly carrying out plasma brushing on the surface of the copper foil on the C for 5 minutes by using a plasma brushing machine, then horizontally fixing the C and a special clamp in a film plating machine in a matching way, and evaporating a layer on the surface of the copper foil on the C

Chromium (iv) is designated as D;

2.2) taking the D out of the film coating machine, and carrying out plasma brushing on the surface of the chromium film layer on the D for 5 minutes by using a plasma brushing machine.

The step 3) comprises the following specific steps:

3.1) placing D on a spin coater, uniformly coating a layer of tackifier primer solution HMDS on the chromium surface of D, then running for 3 seconds at 500 revolutions per second, and then running for 30 seconds at 5000 revolutions per second for spin coating with a layer of photoresist AZ6130, which is called E;

3.2) prebaking: placing the E on a hot plate, baking the E for 2 minutes at 100 ℃, and transferring the E to a photoetching machine;

3.3) photoetching: the exposure time of the photoetching machine is set to be 3.9s, and the exposure intensity is set to be 30mW/cm²Exposing the photoresist on the surface E;

3.4) developing: placing the exposed E in a prepared ZX238 developing solution for developing for 25s, cleaning with deionized water, and blow-drying with nitrogen, wherein the F is called;

3.5) hardening: and F is placed on a hot plate, baked for 3 minutes at 120 ℃ and subjected to photoresist hardening treatment.

The step 4) comprises the following specific steps:

4.1) preparing cerium ammonium nitrate corrosive liquid, placing F into the corrosive liquid, and corroding for 90 seconds under the condition of water bath at 30 ℃;

4.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun.

The step 5) comprises the following specific steps:

5.1) preparing a copper corrosive liquid, placing F into the copper corrosive liquid, and corroding for 120 seconds under the condition of water bath at 40 ℃;

and 5.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun to obtain the product G.

The step 6) comprises the following specific steps:

6.1) placing the G on a rotating table, uniformly spraying an acetone solution on the surface of the G, and removing the photoresist on the G, namely H;

6.2) putting H into cerium ammonium nitrate corrosive liquid, corroding for 10 minutes in a water bath at the temperature of 30 ℃, and taking out the H after chromium is completely corroded to be I;

6.3) cleaning the I with deionized water, and drying with a nitrogen gun;

6.4) soaking the I in an acetone solution to dissolve the photoresist between the copper foil and the glass substrate;

6.5) removing the copper grid from the glass substrate, and carrying out cleaning and drying treatment.

The step 7) comprises the following specific steps:

7.1) electroplating a layer of nickel on the surface of the copper grid mesh for anti-oxidation protection, and finishing the accelerated grid mesh manufacturing.

The invention has the advantages that:

1) the invention relates to a method for plating nickel on the surface of a copper foil and photoetching a nickel pattern to be used as a mask on the surface of the copper foil, which solves the problem that a complete acceleration grid can not be manufactured due to weak adhesion between the copper foil and a photoresist;

2) the invention provides a high-transmittance fringe image converter grid and a preparation method thereof, which meet the requirements, the traditional grid opening ratio is below 49%, the grid opening ratio designed by the invention is between 53.8% and 68.2%, the prepared grid has higher transmittance, the number of signal electrons is increased, the signal-to-noise ratio of the fringe image converter is improved, and the shape and the size are shown in figure 2;

3) the grid and the method can be applied to the preparation of the accelerating grid used by electronic optical instruments such as stripe cameras, framing cameras, electron diffractometers, ion energy analyzers, scanning electron microscopes, ion accelerators and the like.

Drawings

FIG. 1 is a flow chart of the manufacturing process of the accelerated grid mesh of the high transmittance stripe image converter tube of the present invention;

FIG. 2 is a schematic diagram of the structure and size of a photolithography mask used in the method for preparing a high transmittance fringe image converter accelerating grid.

Detailed Description

The invention is further described below with reference to the accompanying drawings.

As shown in fig. 1, a method for preparing an accelerating grid of a high-transmittance fringe image converter tube comprises the following steps:

1) preparing raw materials, namely photoetching a mask plate, copper foil with the thickness of 3-6 mu m, and flatly adhering the copper foil on a glass substrate by using photoresist and a cylindrical rolling tool;

2) plating a film, including evaporating chrome on the surface of the copper foil and performing plasma cleaning on the surface of the chrome;

3) photoetching, including coating a layer of tackifier primer solution on the chromium surface, then uniformly coating a layer of photoresist, prebaking, photoetching, developing and hardening;

4) wet etching of chromium;

5) wet etching of copper;

6) removing the chromium film and the photoresist;

7) electroplating a layer of nickel on the surface of the copper grid.

The specific steps of the step 1) are as follows:

1.1) designing and manufacturing a photoetching mask plate of a corresponding pattern when the opening ratio of a grid mesh is 53.8% -68.2%, wherein the structure and the size are shown as the attached figure 2: the grid mesh is formed by periodically repeating hollow grids and grid bars, the size A of each hollow grid is 19-22 mu m, and the size B of each grid bar is 4-8 mu m;

1.2) cutting a double-sided polished electrolytic copper foil with the thickness of 3-6 microns well by laser cutting, pickling with a solution prepared from 50ml of glacial acetic acid, 150g of sodium chloride, 25ml of hydrochloric acid and 500ml of deionized water, and then ultrasonically cleaning and drying with deionized water;

1.3) applying the copper foil to the glass substrate by means of photoresist and a cylinder rolling tool, and is named C.

The specific steps of the step 2) are as follows:

2.1) firstly carrying out plasma brushing on the surface of the copper foil on the C for 5 minutes by using a plasma brushing machine, then horizontally fixing the C and a special clamp in a film plating machine in a matching way, and evaporating a layer on the surface of the copper foil on the C

Chromium (iv) is designated as D;

2.2) taking the D out of the film coating machine, and carrying out plasma brushing on the surface of the chromium film layer on the D for 5 minutes by using a plasma brushing machine.

The step 3) comprises the following specific steps:

3.1) placing D on a spin coater, uniformly coating a layer of tackifier primer solution HMDS on the chromium surface of D, then running for 3 seconds at 500 revolutions per second, and then running for 30 seconds at 5000 revolutions per second for spin coating with a layer of photoresist AZ6130, which is called E;

3.2) prebaking: placing the E on a hot plate, baking the E for 2 minutes at 100 ℃, and transferring the E to a photoetching machine;

3.3) photoetching: the exposure time of the photoetching machine is set to be 3.9s, and the exposure intensity is set to be 30mW/cm²Exposing the photoresist on the surface E;

3.4) developing: placing the exposed E in a prepared ZX238 developing solution for developing for 25s, cleaning with deionized water, and blow-drying with nitrogen, wherein the F is called;

3.5) hardening: and F is placed on a hot plate, baked for 3 minutes at 120 ℃ and subjected to photoresist hardening treatment.

The step 4) comprises the following specific steps:

4.1) preparing cerium ammonium nitrate corrosive liquid, placing F into the corrosive liquid, and corroding for 90 seconds under the condition of water bath at 30 ℃;

4.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun.

The step 5) comprises the following specific steps:

5.1) preparing a copper corrosive liquid, placing F into the copper corrosive liquid, and corroding for 120 seconds under the condition of water bath at 40 ℃;

and 5.2) taking out the F, cleaning the F by using deionized water, and drying the F by using a nitrogen gun to obtain the product G.

The step 6) comprises the following specific steps:

6.1) placing the G on a rotating table, uniformly spraying an acetone solution on the surface of the G, and removing the photoresist on the G, namely H;

6.2) putting H into cerium ammonium nitrate corrosive liquid, corroding for 10 minutes in a water bath at the temperature of 30 ℃, and taking out the H after chromium is completely corroded to be I;

6.3) cleaning the I with deionized water, and drying with a nitrogen gun;

6.4) soaking the I in an acetone solution to dissolve the photoresist between the copper foil and the glass substrate;

6.5) removing the copper grid from the glass substrate, and carrying out cleaning and drying treatment.

The step 7) comprises the following specific steps:

7.1) electroplating a layer of nickel on the surface of the copper grid mesh for anti-oxidation protection, and finishing the accelerated grid mesh manufacturing.