CN114220721A - Method for obtaining atomic-level cleanliness of GaAs photocathode - Google Patents

Method for obtaining atomic-level cleanliness of GaAs photocathode Download PDF

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CN114220721A
CN114220721A CN202111531550.2A CN202111531550A CN114220721A CN 114220721 A CN114220721 A CN 114220721A CN 202111531550 A CN202111531550 A CN 202111531550A CN 114220721 A CN114220721 A CN 114220721A
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吴波
赵林
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Shenzhen Ronger Optic & Electronic Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
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Abstract

The invention discloses a method for obtaining atomic-level cleanliness of a GaAs photoelectric cathode, which comprises the following steps of carrying out low-temperature thermal cleaning, ion stripping, atomic hydrogen reduction and the like to obtain an activated surface with atomic-level cleanliness, wherein the method comprises the following specific steps of: s1: low-temperature thermal cleaning: the low-temperature thermal cleaning adopts a radiation heating mode, the heating wire is heated to generate thermal radiation, and the thermal radiation penetrates through the AVG glass and then irradiates the GaAs epitaxial layer to heat the GaAs epitaxial layer; by adopting the scheme, the product performance can be obviously improved, the material cost is reduced, and the cost is controlled by adopting low-temperature heat cleaning, so that on one hand, the requirement of AVG glass in the GaAs photocathode is reduced, thus 7056 glass with higher cost performance can be adopted for substitution, and the cost of a single material is reduced by about 50%; on the other hand, the 7056 glass is adopted, so that the bonding temperature is lower, the requirement on a bonding process is reduced, and the bonding yield is improved.

Description

Method for obtaining atomic-level cleanliness of GaAs photocathode
Technical Field
The invention relates to the field of GaAs photocathode devices, in particular to a method for obtaining atomic-level cleanliness of a GaAs photocathode.
Background
At present, international colleges, research institutes and companies researching the GaAs photocathode of three generations are countless, but only a few countries (America, Russia and the like) realize the mass production of the three generations of image tubes. The main factor limiting the mass production is the GaAs photocathode, one of the key processes for preparing the GaAs photocathode is the acquisition of atomic-level cleanliness, which is the most difficult process in the whole preparation process of the low-light-level image intensifier, and the performance and the qualification rate of the third-generation image tube are greatly influenced. (the main three indexes for describing the GaAs photocathode are integral sensitivity, radiation sensitivity and uniformity, and the three indexes are the core technical indexes of three generation image tubes.
The known GaAs photoelectric cathode atomic-level cleanliness obtaining process mostly adopts a high-temperature thermal cleaning mode, and the whole GaAs photoelectric cathode is heated by adopting a thermal radiation mode in a vacuum environment, so that oxides on the surface are decomposed, a GaAs layer which is easy to emit electrons is leaked out, and the following 4 problems exist:
1) the performance is low: the method needs higher temperature (about 600 ℃) in the preparation process, arsenic oxide and gallium oxide can be decomposed by the high temperature, but the decomposition temperature of the gallium oxide is approximate to that of the gallium arsenide, the gallium arsenide can be decomposed by inaccurate control, gallium drops are formed on the surface, the surface rich in gallium is not beneficial to activating the emission of electrons, and the performance of the product is reduced;
2) the percent of pass is low: before the atomic cleanliness is obtained, the GaAs photocathode can undergo various processes such as epitaxial growth, high-temperature bonding, directional corrosion, film coating and the like, so that the consistency of the surface of the product is poor, and when the method is adopted for processing, different samples need to absorb different heat and time, but the judgment is difficult in the actual operation process, so that the qualification rate of the GaAs photocathode is low;
3) poor uniformity: the high-temperature thermal cleaning can damage the structure of the whole emitting layer to cause the change of local components, the uniformity of a light source is not easy to control, and the uniformity difference of the emitting layer of the product can be caused, which is reflected in that part of the emitting layer is bright and part of the emitting layer is dark;
4) the cost is high: the gallium arsenide photocathode is formed by bonding AVG glass and a GaAs epitaxial wafer, and because a high-temperature mode is adopted for thermal cleaning, the requirements on the transition point and the softening point of the glass are high on one hand, and the requirements on the bonding process are strict on the other hand, so that the raw material cost and the labor cost are increased.
Disclosure of Invention
In order to overcome the defects of low performance, low production qualified rate, poor uniformity of an emitting layer and high production cost of a photoelectric cathode in the prior art, the invention provides the method for obtaining the atomic-level cleanliness of the GaAs photoelectric cathode, which effectively solves the problems of gallium arsenide decomposition, component change and raw material cost rise caused by overhigh temperature in the process of obtaining the atomic-level cleanliness by a low-temperature thermal cleaning technology, a plasma stripping technology and an atomic hydrogen cleaning technology.
In order to solve the technical problems, the invention provides the following technical scheme: a method for obtaining atomic-level cleanliness of a GaAs photocathode comprises the following steps of carrying out low-temperature thermal cleaning, ion stripping, atomic hydrogen reduction and the like to obtain an activated surface with atomic-level cleanliness, wherein the method comprises the following specific steps:
s1: low-temperature thermal cleaning: the low-temperature thermal cleaning adopts a radiation heating mode, the heating wire is heated to generate thermal radiation, and the thermal radiation penetrates through the AVG glass and then irradiates the GaAs epitaxial layer to heat the GaAs epitaxial layer;
s2 argon ion stripping: the ionized Ar + is accelerated by the emission voltage, so that the Ar + has larger kinetic energy to bombard the surface of the sample, and the molecular structure is damaged, thereby realizing the stripping of the surface; by stripping the argon ions, substances with surfaces which are not easy to decompose by heat, such as gallium oxide, carbon and other oxides, can be effectively removed, and the surfaces can be polished to improve the micro roughness of the surfaces, so that preparation is provided for the next cesium-oxygen activation of the GaAs photocathode;
s3: atomic hydrogen cleaning: the hydrogen atom gun generates atomic hydrogen in a thermal cracking mode, local high temperature is generated under the action of the atomic hydrogen, harmful substances such as residual carbon, gallium oxide and the like on the surface of the GaAs emission layer are removed through reaction, the evaporation point of the generated gallium monoxide is low, and the generated gallium monoxide can be easily sublimated, so that the clean and activated GaAs emission layer is exposed.
After a sample enters from one valve, the sample is transmitted to a station through a lifting conversion device, one heat radiation device is started, the power is set to be W1, the working time is T1, an argon atom gun is started, the filament current is set to be I1, the grid voltage is set to be U1, the emission voltage is set to be U2, the working time is T2, then the sample is transmitted to another station through the lifting conversion device, a hydrogen atom gun is started, the filament current is set to be I2, the working time is T3, after the designated time, the sample is cleaned, and the sample is transferred to next process equipment.
In the step S1, the thermal radiation source is placed on the large end face of the AVG, the distance from the large end face to the GaAs epitaxial layer is 6-20 mm, the working power W1 of the heating wire is 60-100W, the working time T1 is 30-60 min, and the reaction in the low-temperature thermal cleaning process is disclosed as follows:
Figure BDA0003410976310000041
Figure BDA0003410976310000042
Figure BDA0003410976310000043
as a preferred technical solution of the present invention, the step S2 is performed in a high vacuum environment, the range is controlled to be 1 × 10 "5 torr to 1 × 10" 7torr, argon is introduced through a precision leakage valve to control the vacuum degree, argon ions in the high vacuum environment form an electron cloud with a certain density through a metal grid, and the probability of Ar gas colliding with the electron cloud is increased, so that Ar + with a required density is generated, and the filament current I1 of the argon ion gun used in the step S2 is 2.5 to 3.5A, the grid voltage U1 is 150 to 200V, the emission voltage U2 is 2000 to 3000V, the operating time T2 is 10 to 60min, and the stripping speed can be controlled by adjusting the above parameters in practical cases, and the thickness of the stripped GaAs emission layer in the present invention is about 10 to 100 nm.
In a preferred embodiment of the present invention, the hydrogen atom gun used in S3 generates atomic hydrogen by thermal cracking, the filament current I2 is 10 to 15A, the operation time T3 is 5to 30min, and the chemical formula of the harmful substances such as carbon and gallium oxide remaining on the surface is:
Figure BDA0003410976310000044
Figure BDA0003410976310000045
as a preferable aspect of the present invention, the operating temperature of the heat radiation device is set to 400 ℃.
As a preferred technical scheme of the invention, the high vacuum environment in S2 includes but is not limited to that the vacuum degree of the ultrahigh vacuum chamber can be less than or equal to 1 x 10 < -9 > torr when no load exists, the effective working distance of the argon ion gun is 50-200 mm, the effective working area is more than or equal to 20mm, the stripping speed is more than or equal to 0.5nm/min, the filament current of the hydrogen ion gun is more than or equal to 10A, and the maximum temperature is more than or equal to 1500 ℃.
Compared with the prior art, the invention can achieve the following beneficial effects:
1. by adopting the scheme, the product performance can be obviously improved, the material cost is reduced, and the cost is controlled by adopting low-temperature heat cleaning, so that on one hand, the requirement of AVG glass in the GaAs photocathode is reduced, thus 7056 glass with higher cost performance can be adopted for substitution, and the cost of a single material is reduced by about 50%; on the other hand, the 7056 glass is adopted, so that the bonding temperature is lower, the requirement on a bonding process is reduced, and the bonding yield is improved.
2. The method effectively reduces the qualification rate problem caused by poor consistency of the gallium arsenide cathode by reducing the thermal cleaning temperature, and obviously improves the qualification rate of cathode activation because the method integrally improves the performance of the gallium arsenide cathode, thereby improving the qualification rate of finished products and reducing the cost.
Drawings
FIG. 1 is a schematic structural diagram according to a first embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a working device according to the present invention;
FIG. 3 is a top view of the construction of the working device of the present invention;
FIG. 4 is a flow chart of a structure according to a first embodiment of the present invention;
FIG. 5 is a schematic structural view of the low temperature thermal cleaning of step S1 according to the present invention.
1. A gas analysis device; 2. a hydrogen atom gun; 3. an argon atom gun; 4. a lifting transmission device; 5. a valve; 6. and a heat radiation device.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of facilitating an understanding of technical means, characteristics of creation, objectives and functions realized by the present invention, but the following embodiments are only preferred embodiments of the present invention, and are not intended to be exhaustive. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The first embodiment is as follows:
as shown in fig. 1, a method for obtaining atomic-level cleanliness of a GaAs photocathode includes performing low-temperature thermal cleaning, ion stripping, atomic hydrogen reduction, and the like to obtain an activated surface with atomic-level cleanliness, and the principle of the specific steps is as follows:
s1: low-temperature thermal cleaning: the low-temperature thermal cleaning adopts a radiation heating mode, the heating wire is heated to generate thermal radiation, and the thermal radiation penetrates through the AVG glass and then irradiates the GaAs epitaxial layer to heat the GaAs epitaxial layer;
s2 argon ion stripping: the ionized Ar + is accelerated by the emission voltage, so that the Ar + has larger kinetic energy to bombard the surface of the sample, and the molecular structure is damaged, thereby realizing the stripping of the surface;
s3: atomic hydrogen cleaning: the hydrogen atom gun generates atomic hydrogen in a thermal cracking mode, local high temperature is generated under the action of the atomic hydrogen, harmful substances such as residual carbon, gallium oxide and the like on the surface of the GaAs emission layer are removed through reaction, the evaporation point of the generated gallium monoxide is low, and the generated gallium monoxide can be easily sublimated, so that the clean and activated GaAs emission layer is exposed.
After a sample enters from a valve 5, the sample is transmitted to a station through a lifting conversion device 4, a heat radiation device 6 is started, the power is set to be W1, the working time is T1, an argon atom gun 3 is started, the filament current I1 is set, the grid voltage U1, the emission voltage is U2, the working time is T2, the sample is transmitted to another station through the lifting conversion device 4, a hydrogen atom gun 2 is started, the filament current I2 is set, the working time is T3, after the designated time, the sample is cleaned, the sample is transferred to next process equipment, and when the sample is used, the interior of the sample is analyzed through a gas analysis device 1 in real time.
In other embodiments, in step S1, the thermal radiation source is placed on the large end face of the AVG, the distance from the large end face of the GaAs epitaxial layer is 6-20 mm, the operating power W1 of the heating wire is 60-100W, the operating time T1 is 30-60 min, and the reaction in the low-temperature thermal cleaning process is disclosed as follows:
Figure BDA0003410976310000071
Figure BDA0003410976310000072
Figure BDA0003410976310000073
in other embodiments, the S2 step needs to be performed in a high vacuum environment, the range is controlled to be 1 × 10 "5 torr to 1 × 10" 7torr, the vacuum degree is controlled by introducing argon through a precision leakage valve, argon ions in the high vacuum form an electron cloud with a certain density through a metal gate, and the probability of collision between Ar gas and the electron cloud is increased, so that Ar + with a required density is generated, and the filament current I1 of the argon ion gun used in the S2 step is 2.5 to 3.5A, the gate voltage U1 is 150 to 200V, the emission voltage U2 is 2000 to 3000V, the working time T2 is 10 to 60min, and the stripping speed can be controlled by adjusting the above parameters in practical cases, wherein the thickness of the stripped GaAs emission layer in the present invention is about 10 to 100 nm.
In another embodiment, the hydrogen atom gun used in S3 generates atomic hydrogen by thermal cracking, the filament current I2 is 10 to 15A, the operation time T3 is 5to 30min, and the chemical formula of the residual harmful substances such as carbon and gallium oxide on the surface is:
Figure BDA0003410976310000081
Figure BDA0003410976310000082
in other embodiments, the operating temperature is set to 400 ℃ or higher in the heat radiation device.
In other embodiments, the high vacuum environment in S2 includes, but is not limited to, an ultra-high vacuum chamber with no load, the vacuum degree can be less than or equal to 1 × 10-9torr, the effective working distance of the argon ion gun is 50-200 mm, the effective working area is greater than or equal to 20mm, the stripping speed is greater than or equal to 0.5nm/min, the filament current of the hydrogen ion gun is greater than or equal to 10A, and the maximum temperature is greater than or equal to 1500 ℃.
Example two:
in this embodiment, on the basis of the first embodiment, the using effect can be achieved by adjusting the process sequence, including performing argon ion stripping, performing low-temperature thermal cleaning, and performing atomic hydrogen cleaning, or performing low-temperature thermal cleaning, performing atomic hydrogen cleaning, and performing argon ion stripping.
By adopting the scheme, the product performance can be obviously improved, and the material cost is reduced:
the performance: the performance parameters for measuring the sensitivity of the GaAs photocathode mainly comprise integral sensitivity, radiation sensitivity and uniformity, and are shown in the following table
TABLE 1 Performance enhancement comparison
Figure BDA0003410976310000091
Secondly, cost:
the cost control adopts low-temperature thermal cleaning, so that on one hand, the requirement of AVG glass in the GaAs photocathode is reduced, and thus 7056 glass with higher cost performance can be used for substitution, and the cost of a single material is reduced by about 50%; on the other hand, the 7056 glass is adopted, so that the bonding temperature is lower, the requirement on a bonding process is reduced, and the bonding yield is improved.
And secondly, the problem of qualification rate caused by poor consistency of the gallium arsenide cathode is effectively reduced by reducing the thermal cleaning temperature, and the method improves the performance of the gallium arsenide cathode on the whole, so that the qualification rate of cathode activation is obviously improved, the qualification rate of finished products is improved, and the cost is reduced.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. A method for obtaining the atomic-level cleanliness of a GaAs photocathode is characterized by comprising the following steps: the method comprises the following steps of carrying out low-temperature thermal cleaning, ion stripping, atomic hydrogen reduction and the like to obtain an activated surface with atomic-level cleanliness, wherein the principle of the specific steps is as follows:
s1: low-temperature thermal cleaning: the low-temperature thermal cleaning adopts a radiation heating mode, the heating wire is heated to generate thermal radiation, and the thermal radiation penetrates through the AVG glass and then irradiates the GaAs epitaxial layer to heat the GaAs epitaxial layer;
s2 argon ion stripping: the ionized Ar + is accelerated by the emission voltage, so that the Ar + has larger kinetic energy to bombard the surface of the sample, and the molecular structure is damaged, thereby realizing the stripping of the surface;
s3: atomic hydrogen cleaning: the hydrogen atom gun generates atomic hydrogen in a thermal cracking mode, local high temperature is generated under the action of the atomic hydrogen, harmful substances such as residual carbon, gallium oxide and the like on the surface of the GaAs emission layer are removed through reaction, the evaporation point of the generated gallium monoxide is low, and the generated gallium monoxide can be easily sublimated, so that the clean and activated GaAs emission layer is exposed.
After a sample enters from one valve, the sample is transmitted to a station through a lifting conversion device, one heat radiation device is started, the power is set to be W1, the working time is T1, an argon atom gun is started, the filament current is set to be I1, the grid voltage is set to be U1, the emission voltage is set to be U2, the working time is T2, then the sample is transmitted to another station through the lifting conversion device, a hydrogen atom gun is started, the filament current is set to be I2, the working time is T3, after the designated time, the sample is cleaned, and the sample is transferred to next process equipment.
2. The method for obtaining atomic-level cleanliness of a GaAs photocathode according to claim 1, wherein: in the step S1, the heat radiation source is placed on the large end face of the AVG and is 6-20 mm away from the GaAs epitaxial layer, the working power W1 of the heating wire is 60-100W, the working time T1 is 30-60 min, and the reaction in the low-temperature heat cleaning process is disclosed as follows:
Figure FDA0003410976300000021
Figure FDA0003410976300000022
Figure FDA0003410976300000023
3. the method for obtaining atomic-level cleanliness of a GaAs photocathode according to claim 1, wherein: the step S2 needs to be performed in a high vacuum environment, the range is controlled to be 1 × 10-5torr to 1 × 10-7torr, argon is introduced through a precision leakage valve to control the vacuum degree, argon ions in the high vacuum form electron clouds with a certain density through a metal grid, the probability of collision between Ar gas and the electron clouds is increased, so that Ar + with a required density is generated, the filament current I1 of the argon ion gun used in the step S2 is 2.5-3.5A, the grid voltage U1 is 150-200V, the emission voltage U2 is 2000-3000V, the working time T2 is 10-60 min, the stripping speed can be controlled by adjusting the above parameters in practical situations, and the thickness of the stripped GaAs emission layer in the invention is about 10-100 nm.
4. The method for obtaining atomic-level cleanliness of a GaAs photocathode according to claim 1, wherein: the hydrogen atom gun adopted in the S3 generates atomic hydrogen through a thermal cracking mode, the filament current I2 is 10-15A, the working time T3 is 5-30 min, and the chemical formula of the residual harmful substances such as carbon, gallium oxide and the like on the surface is as follows:
Figure FDA0003410976300000024
Figure FDA0003410976300000025
5. the method for obtaining atomic-level cleanliness of a GaAs photocathode according to claim 1, wherein: the working temperature of the heat radiation device is set to be more than 400 ℃.
6. The method for obtaining atomic-scale cleanliness of a GaAs photocathode according to claim 3, wherein: the high vacuum environment in S2 includes, but is not limited to, that the vacuum degree of the ultra-high vacuum chamber is not more than 1 x 10 < -9 > torr when no load exists, the effective working distance of the argon ion gun is 50-200 mm, the effective working area is not less than 20mm, the stripping speed is not less than 0.5nm/min, the filament current of the hydrogen ion gun is not less than 10A, and the maximum temperature is not less than 1500 ℃.
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