CN215757620U - Corrosion device of germanium sheet or germanium spindle - Google Patents
Corrosion device of germanium sheet or germanium spindle Download PDFInfo
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- CN215757620U CN215757620U CN202121822504.3U CN202121822504U CN215757620U CN 215757620 U CN215757620 U CN 215757620U CN 202121822504 U CN202121822504 U CN 202121822504U CN 215757620 U CN215757620 U CN 215757620U
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Abstract
The utility model provides a germanium sheet or germanium ingot corrosion device, which comprises a corrosion cylinder; a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0; the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body; and a heater is arranged below the corrosion cylinder. The device sets up the toper arch, reduces germanium raw materials and corrosion unit's area of contact for corrode thoroughly, the corrosion effect is better. The germanium material is far away from the heater below the corrosion cylinder body, is heated uniformly, and reduces the generation of cracks.
Description
Technical Field
The utility model belongs to the field of material surface corrosion, and particularly relates to a corrosion device for a germanium sheet or a germanium ingot.
Background
The preparation of infrared grade germanium single crystal or detector grade high-purity germanium has high requirement on the purity of the germanium raw material, and before purification, the germanium raw material needs to be subjected to surface corrosion treatment to remove an oxide layer and some sticky impurities on the surface of the raw material. NaOH and H2O2The proportioning corrosive liquid is a common corrosive system, and when germanium is corroded in the corrosive liquid, the main chemical reaction equation is as follows:
(1)Ge+H2O2＝GeO+H2O
(2)GeO+H2O2＝GeO2+H2O
(3)GeO2+H2O＝H2GeO3
(4)H2GeO3+NaOH＝Na2GeO3+H2O
(5)2H2O2＝2H2O+O2
GeO2dissolution in water is a relatively slow process, H2O2Low concentration of (A) slow reaction, low corrosion efficiency, H2O2At higher concentrations, both equations (1) and (2) are exacerbated, in the presence of GeO2As it is formed, it coats the surface of the GeO, preventing further contact of the germanium and the oxidizing agent. While following H2O2Increase of concentration, extension of etching time, and formation of GeO2When the thickness of the germanium is thicker and thicker, a layer of insoluble white precipitate is formed on the surface of the germanium; in the corrosion and cleaning processes, if factors such as poor temperature control and uniform heat are adopted, the germanium material is easy to crack under the action of stress.
The chemical property of germanium is relatively stable, but when the germanium material is placed in the air, particularly under the condition of high temperature, the germanium material can be in contact with oxygen and water vapor in the air to generate slow oxidation reaction, and oxide is generated to be attached to the surface of the germanium material. Germanium is a brittle and hard substance, and if the corrosion device is not arranged reasonably, the germanium raw material is easy to collide with the corrosion device in the process of placing the germanium raw material or corroding, so that the corrosion device is damaged or the germanium raw material is crushed.
SUMMERY OF THE UTILITY MODEL
In view of the above, the present invention provides an etching apparatus for germanium wafers or germanium ingots, which has a good etching effect on germanium raw materials.
The utility model provides a germanium sheet or germanium ingot corrosion device, which comprises a corrosion cylinder body;
a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0;
the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body;
and a heater is arranged below the corrosion cylinder.
Preferably, the conical protrusions and the holes are arranged in rows, and two adjacent rows of the conical protrusions are spaced by one row of the holes.
Preferably, the conical projection is a pyramid or a cone.
Preferably, the distance between every two adjacent conical protrusions is 20-30 mm, and the vertical height of each conical protrusion is 3-5 mm;
the distance between adjacent holes is 20-30 mm, and the diameter of each hole is 4.5-5.5 mm.
Preferably, the etching cylinder further comprises a support rod for supporting the pad;
the support rod is arranged at the bottom of the inner cavity of the corrosion cylinder body.
Preferably, the backing plate is provided with a plurality of layers, and two adjacent layers are separated by the support rod.
Preferably, the upper part of the side wall of the corrosion cylinder is provided with a water overflow port;
a water outlet arranged on the side wall of the corrosion cylinder between the base plate and the bottom of the corrosion cylinder, and a water outlet pipe connected with the water outlet; and the water outlet pipe is provided with a water outlet flow meter.
Preferably, the system also comprises a water inlet pipe, wherein a water inlet flowmeter is arranged on the water inlet pipe;
the water inlet pipe provides water for the corrosion cylinder.
The utility model provides a germanium sheet or germanium ingot corrosion device, which comprises a corrosion cylinder body; a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0; the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body; and a heater is arranged below the corrosion cylinder. The device sets up the toper arch, reduces germanium raw materials and corrosion unit's area of contact for corrode thoroughly, the corrosion effect is better. The germanium material is far away from the heater below the corrosion cylinder body, is heated uniformly, and reduces the generation of cracks.
Drawings
Fig. 1 is a schematic structural diagram of a germanium wafer or germanium ingot etching device provided by the present invention, wherein 1 is an etching cylinder, 2 is a water inlet, 21 is a water inlet flow meter, 3 is a backing plate, 31 is a hole, 32 is a conical protrusion, 33 is a support rod, 4 is a water outlet, 41 is a water outlet flow meter, 5 is a heater, and 6 is an overflow port.
Detailed Description
The utility model provides a germanium sheet or germanium ingot corrosion device, which comprises a corrosion cylinder body;
a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0;
the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body;
and a heater is arranged below the corrosion cylinder.
In the utility model, the corrosion device comprises a corrosion cylinder body, and a base plate is arranged in the corrosion cylinder body; the germanium sheet or the germanium ingot is placed on the base plate as a germanium raw material to be corroded, and the base plate is made of PTFE.
The base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body; the conical bulge is preferably a pyramid or a cone; the conical protrusion can minimize the contact area between the germanium raw material and the corrosion device, so that the corrosion is thorough and the corrosion effect is good.The conical protrusions and the holes are arranged in rows, and two adjacent rows of the conical protrusions are spaced by one row of the holes. In the utility model, the distance between adjacent conical bulges is 20-30 mm, and the vertical height of each conical bulge is 3-5 mm; the distance between adjacent holes is 20-30 mm, and the diameter of each hole is 4.5-5.5 mm. In a specific embodiment, the area of the backing plate is 300-350 cm2. The number of piles of backing plate is the one deck, and the bottom distance apart from corroding the barrel is 45mm, is equipped with triangular pyramid and hole on the backing plate, adjacent two rows through one row between the triangular pyramid the hole interval, the vertical height of triangular pyramid is 4mm, and the interval of two adjacent triangular pyramids is 25mm, and the diameter in every hole is 5mm, and the distance in two adjacent holes is 25 mm.
Preferably, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder body, and the preset distance is greater than 0; the backing plate preferably realizes required preset distance through the bracing piece, the bracing piece is used for making the backing plate, the bracing piece is installed corrode the inner chamber bottom of barrel. In a specific embodiment, the preset distance is preferably 40-50 mm.
In the utility model, the number of the backing plate can be one or multiple; if the backing plate is provided with a plurality of layers, the two adjacent layers are separated by the supporting rod. Through setting up the multilayer backing plate, can once only corrode more germanium raw materials, improve corrosion efficiency.
In the utility model, the upper part of the side wall of the corrosion cylinder is provided with an overflow port; in a specific embodiment, the overflow port is arranged at a position 20-30 mm below the upper edge of the corrosion cylinder body, so that boiling liquid is prevented from flowing out of the corrosion cylinder body in the corrosion process. In a specific embodiment, the overflow port is arranged 25mm below the upper edge of the corrosion cylinder.
The water outlet is arranged on the side wall of the corrosion cylinder between the base plate and the bottom of the corrosion cylinder, and the water outlet pipe is connected with the water outlet; the water outlet pipe is provided with a water outlet flowmeter and a water outlet switch; the water outlet flow meter and the water outlet switch control the flow of the water outlet. If the base plates are arranged in multiple layers, the water outlet is positioned on the bottom base plate and the side wall of the corrosion cylinder at the bottom of the corrosion cylinder.
In the utility model, the corrosion device also comprises a water inlet pipe, and a water inlet flowmeter is arranged on the water inlet pipe; the water inlet pipe provides inlet water for the corrosion cylinder; the inlet water is preferably 18 megaohm high-purity water.
In the utility model, a heater is arranged below the corrosion cylinder. The heater is used for heating the corrosive liquid and the cleaning liquid.
In the utility model, the method for corroding the germanium sheet or the germanium ingot by adopting the corrosion device comprises the following steps:
placing a germanium raw material to be corroded on a base plate in the corrosion cylinder;
injecting water into the corrosion cylinder through a water inlet pipe, stopping injecting water until 3/4 of the corrosion cylinder, starting heating, adding an alkaline substance when the water temperature reaches 80-100 ℃, stopping heating after reacting for 4-8 min, simultaneously starting water inlet and water outlet, flushing for 3-5 min, and closing the water inlet and the water outlet;
starting heating, adding alkaline substances for dissolving after the water temperature reaches 80-100 ℃, and adding H in portions2O2Stopping heating, simultaneously feeding water and discharging water, flushing for 3-5 min, and closing the water feeding and discharging;
starting heating again, adding an alkaline substance when the water temperature reaches 80-100 ℃, reacting for 4-8 min, stopping heating, simultaneously feeding water and discharging water, flushing for 3-5 min, and closing the feeding water and the discharging water;
continuously starting heating, stopping heating when the water temperature reaches 80-100 ℃, simultaneously feeding water and discharging water for the first time, flushing for the first time when the water feeding temperature is 50-60 ℃, and simultaneously closing the water feeding and discharging; simultaneously feeding water and discharging water for the second time, wherein the water feeding temperature is 30-40 ℃, flushing for the second time, and simultaneously closing the water feeding and the water discharging; and simultaneously feeding water and discharging water for the third time, wherein the water feeding temperature is 10-20 ℃, washing for the third time, simultaneously closing the water feeding and discharging water, taking out the germanium raw material, and drying to finish the corrosion process.
In this application, wait to corrode germanium material and should unify when filling and keep flat or put vertically, can not have the contact between the germanium material. In the embodiment, the weight of the germanium material is 5-10 kg.
This application through the inlet tube to corrode water injection in the barrel, extremely the 3/4 department of corroding the barrel stops the water injection, opens the heating, treats temperature to 80 ~ 100 ℃, adds alkaline substance, stops the heating after reacting 4 ~ 8min, opens simultaneously and intakes and go out water, washes 3 ~ 5min, closes intake and go out water. The process is a pretreatment for corroding the germanium material. In the present application, water injection is preferably to 3/4 of the corrosion cylinder. In the embodiment, about 5-7L of water is injected. In the utility model, 5-10 kg of germanium raw material to be treated is taken as a reference, and the mass of NaOH added in the pretreatment is preferably 2-3 g; or adding 3-4 g of KOH; in the specific embodiment, the mass of NaOH added is 2.5 g; or 3.5g of KOH was added. And simultaneously feeding water and discharging water, wherein the water flow is 2-3L/min, and the water feeding flow is preferably equal to the water discharging flow. The water inlet temperature is preferably 50-60 ℃. The utility model adopts alkaline substances to pretreat the germanium material, removes dirty materials and oxides on the surface, discharges the dirty materials and the oxides, and does not pollute the subsequent corrosive liquid.
After pretreatment, the application starts heating, when the water temperature reaches 80-100 ℃, alkaline substances are added for dissolution, and then H is added in several times2O2And stopping heating, simultaneously feeding water and discharging water, flushing for 3-5 min, and closing the water feeding and discharging. The process is the etching process of the germanium material. After pretreatment, the amount of liquid inside the etch cylinder remained 3/4 of the volume of the etch cylinder. According to the method, 5-10 kg of germanium raw material to be treated is taken as a reference, preferably, when the water temperature reaches 80-100 ℃, alkaline substances are added, and after the alkaline substances are completely dissolved, H is added2O230-40 mL, reacting for 2-3 min, and adding H for the second time2O230-40 mL, reacting for 2-3 min, and adding H for the third time2O230-40 mL, and reacting for 2-3 min. And after the heating is stopped, simultaneously feeding water and discharging water, wherein the temperature of the fed water is 50-60 ℃, the water flow is 2-3L/min, and the flow of the fed water is equal to the flow of the discharged water.
H in the above-mentioned etching process2O2Adding in batches to avoid excessive concentration in one-time addition, and H2O2The one-time addition would decompose rapidly, reducing the corrosion efficiency and corrosion effectiveness. In the utility model, alkaline substances are added in the corrosion processThe amount is 5-8 g; in the specific embodiment, the mass of NaOH added is 5.5 g; or the mass of KOH added was 7.7 g.
After the corrosion is finished, the heating is started again, the alkaline substance is added when the water temperature reaches 80-100 ℃, the heating is stopped after the reaction is carried out for 4-8 min, water is fed and discharged at the same time, the water is washed for 3-5 min, and the water feeding and discharging are stopped. The process is a final treatment process of the germanium material, NaOH is adopted for final treatment, and in order to further remove residual oxides and newly generated oxides, the surface of the germanium material is ensured to be thoroughly corroded; in a specific embodiment, the addition amount of NaOH is (2-3) g; the addition amount of the KOH is (3-4) g. The flow rates of inlet water and outlet water are both 2-3L/min, and the flow rates of inlet water and outlet water are equal. The temperature of the inlet water is preferably 50-60 ℃. In the specific embodiment, the flow rates of inlet water and outlet water are 2.5L/min; the amount of NaOH added was 2.5g, or the amount of KOH added was 3.5 g.
After the treatment, the heating is continuously started, the heating is stopped when the water temperature reaches 80-100 ℃, the water is simultaneously fed and discharged for the first time, the water feeding temperature is 50-60 ℃, the water is washed for the first time, and the water feeding and discharging are simultaneously closed; simultaneously feeding water and discharging water for the second time, wherein the water feeding temperature is 30-40 ℃, flushing for the second time, and simultaneously closing the water feeding and the water discharging; and simultaneously feeding water and discharging water for the third time, wherein the water feeding temperature is 10-20 ℃, washing for the third time, simultaneously closing the water feeding and discharging water, taking out the germanium raw material, and drying to finish the corrosion process.
The flow rate of each flushing in the cleaning process is preferably 2-3L/min; in a specific embodiment, the flow rate of the rinse is 2.5L/min. After each shut-off of the inlet and outlet water, the inlet and outlet water is preferably switched on again after 2 min. The volume of liquid in the etch cartridge is preferably maintained at 3/4 of the etch cartridge during the rinse. The temperature gradient is set at the water inlet temperature in the cleaning process, so that the corrosion of the germanium material and the stress generated in the cleaning process are reduced, and the cracks are avoided. The water inlet flow is not less than the water outlet flow, so that the germanium material is prevented from exposing out of corrosive liquid or cleaning liquid; the germanium material can not expose out of the liquid surface in the corrosion and cleaning processes, otherwise, the germanium can be exposed in the air and oxidized when the temperature is higher.
According to the utility model, the germanium raw material is preferably taken out after the cleaning solution completely flows out of the corrosion cylinder. In the utility model, the drying mode is nitrogen blow drying or drying.
In order to further illustrate the present invention, the following describes in detail an etching apparatus for germanium wafer or germanium ingot provided by the present invention with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
S1: weighing a germanium raw material to be corroded, putting the germanium raw material on a PTFE (polytetrafluoroethylene) cushion plate in a corrosion cylinder, and requiring that germanium materials are uniformly placed horizontally or vertically, wherein the germanium materials cannot be contacted with each other, and the weight of the germanium materials reaches 6 kg; the number of piles of backing plate is the one deck, and the bottom distance apart from corroding the barrel is 45mm, is equipped with triangular pyramid and hole on the backing plate, adjacent two rows through one row between the triangular pyramid the hole interval, the vertical height of triangular pyramid is 4mm, and the interval of two adjacent triangular pyramids is 25mm, and the diameter in every hole is 5mm, and the distance in two adjacent holes is 25 mm.
An overflow port is arranged 25mm below the upper edge of the corrosion cylinder, a water outlet is arranged on the side wall of the corrosion cylinder between the base plate and the bottom of the corrosion cylinder, the water outlet is connected with a water outlet pipe, and a water outlet switch and a water outlet flowmeter are arranged on the water outlet pipe; a heater is arranged right below the corrosion cylinder and used for heating the corrosive liquid and the cleaning liquid;
s2: opening a water inlet switch, adding normal-temperature pure water, enabling the water amount to reach three-fourth of the volume of the beaker, closing the water inlet switch, starting heating, adding NaHOH 2.5g when the water in the beaker is slightly boiled (95 ℃) after corrosion, reacting for 6min, closing the heating, simultaneously opening the water inlet switch and the water outlet switch, enabling the water flow to be 2.5L/min, requiring the water inlet flow to be equal to the water outlet flow, enabling the water inlet temperature to be 55 ℃, flushing for 5min, and simultaneously closing the water inlet switch and the water outlet switch;
s3: after S2, ensuring that the water amount is still three-fourth of the volume of the beaker, starting heating, adding 5.5g of NaOH after the water in the beaker is corroded and slightly boils, and adding H after the NaOH is completely dissolved2O2(UP grade, 30%) 35mL, reaction 2.5min, second addition of H2O235mL, react for 2.5min, add H a third time2O235mL, react for 2.5 min; turning off heating, simultaneously turning on a water inlet switch and a water outlet switch, wherein the water flow is 2.5L/min, the water inlet flow is required to be equal to the water outlet flow, the water inlet temperature is 55 ℃, washing for 5min, and then simultaneously turning off the water inlet switch and the water outlet switch;
s4: after S3, ensuring that the water amount is still three-fourth of the volume of the beaker, starting heating, slightly boiling the water in the beaker to be corroded, adding 2.5g of NaOH, reacting for 6min, closing heating, simultaneously opening a water inlet switch and a water outlet switch, ensuring that the water flow is 2.5L/min, requiring that the water inlet flow is equal to the water outlet flow, the water inlet temperature is 55 ℃, flushing for 5min, and simultaneously closing the water inlet switch and the water outlet switch;
s5: after S4, ensuring that the water amount is still three-fourth of the volume of the beaker, starting heating, slightly boiling the water in the beaker after corrosion, closing heating, simultaneously opening a water inlet switch and a water outlet switch, wherein the water flow is 2.5L/min, the water inlet flow is required to be equal to the water outlet flow, the water inlet temperature is 55 ℃, flushing is carried out for 5min, and then simultaneously closing the water inlet switch and the water outlet switch; after 2min, simultaneously opening a water inlet switch and a water outlet switch, wherein the water flow is 2.5L/min, the water inlet flow is required to be equal to the water outlet flow, the water inlet temperature is 35 ℃, washing for 5min, and simultaneously closing the water inlet switch and the water outlet switch; and after 2min, simultaneously opening a water inlet switch and a water outlet switch, wherein the water flow is 2.5L/min, the water inlet flow is required to be equal to the water outlet flow, the water inlet temperature is normal temperature, washing for 10min, closing the water inlet switch, taking out the germanium material after the cleaning liquid completely flows out, drying by using high-purity nitrogen, weighing, and finishing the corrosion process.
Example 2
On the basis of example 1, NaOH was replaced with KOH, and the KOH addition in the pretreatment and the last treatment were 3.5g, respectively, and the KOH addition in the etching treatment was 7.7 g.
Comparative example 1:
compared with the embodiment 1, other operations are unchanged, the shim plate is not provided with the pyramid, and the germanium material is directly placed on the shim plate for corrosion.
Comparative example 2:
compared with the embodiment 1, other operations are unchanged, the small pyramid arranged on the base plate is changed into a small cylinder, and the germanium material is supported on the small cylinder for corrosion.
Comparative example 3:
other operations are unchanged from embodiment 1, step S3H2O2105ml were added in one portion.
Comparative example 4:
the other operations are unchanged from embodiment 1, and the end processing of S4 is cancelled.
Comparative example 5:
compared with example 1, the other operations were not changed, the temperature gradient was not set for the feed water, and normal temperature pure water was used.
If the method adopts a visual inspection mode, the corrosion effect of the corroded germanium material is evaluated, and the corrosion standard is that the surface of the germanium is bright, no white or black oxide exists, and no crack occurs.
TABLE 1 Corrosion Effect of the examples and comparative examples
Under a certain wave band, the transmittance is reduced due to the inclusion of trace oxygen elements, if the method adopts a mode of measuring the infrared transmittance of an optical element on the surface of a corroded germanium sheet or germanium ingot, the corrosion effect of the corroded germanium material is evaluated, and the lower the transmittance is, the poorer the corrosion effect is proved; on the contrary, the better corrosion effect is proved.
TABLE 2 Corrosion Effect of examples and comparative examples
| Transmittance (wavelength 6 μm) | Transmittance (wavelength 10 μm) | |
| Example 1 | 0.485 | 0.491 |
| Example 2 | 0.486 | 0.490 |
| Comparative example 1 | 0.473 | 0.425 |
| Comparative example 2 | 0.479 | 0.446 |
| Comparative example 3 | 0.482 | 0.479 |
| Comparative example 4 | 0.484 | 0.488 |
| Comparative example 5 | 0.485 | 0.490 |
From the above embodiments, the present invention provides an etching apparatus for germanium wafer or germanium ingot, including an etching cylinder; a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0; the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body; and a heater is arranged below the corrosion cylinder. The device sets up the toper arch, reduces germanium raw materials and corrosion unit's area of contact for corrode thoroughly, the corrosion effect is better. The germanium material is far away from the heater below the corrosion cylinder body, is heated uniformly, and reduces the generation of cracks.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The device for corroding the germanium sheet or the germanium ingot is characterized by comprising a corrosion cylinder body;
a base plate is arranged in the corrosion cylinder, a preset distance is arranged between the base plate and the bottom of the corrosion cylinder, and the preset distance is larger than 0;
the base plate comprises a base plate body, and conical bulges and holes which are distributed on the base plate body;
and a heater is arranged below the corrosion cylinder.
2. The etching apparatus of claim 1, wherein said conical projections and said apertures are arranged in rows, adjacent rows of said conical projections being spaced apart by one row of said apertures.
3. The etching apparatus of claim 1, wherein the conical protrusions are pyramids or cones.
4. The etching apparatus according to claim 1, wherein the distance between adjacent conical protrusions is 20 to 30mm, and the vertical height of each conical protrusion is 3 to 5 mm;
the distance between adjacent holes is 20-30 mm, and the diameter of each hole is 4.5-5.5 mm.
5. The etching apparatus of claim 1, wherein the etching cartridge further comprises a support rod for supporting the deck; the supporting rod is arranged at the bottom of the inner cavity of the corrosion cylinder;
the water inlet pipe is provided with a water inlet flowmeter; the water inlet pipe provides water for the corrosion cylinder.
6. The etching apparatus of claim 1, wherein the backing plate is provided in a plurality of layers, and adjacent layers are separated by a support bar.
7. The etching apparatus according to claim 1, wherein an overflow port is provided at an upper portion of a side wall of the etching drum;
the water outlet is arranged on the side wall of the corrosion cylinder between the base plate and the bottom of the corrosion cylinder, and the water outlet pipe is connected with the water outlet; and the water outlet pipe is provided with a water outlet flow meter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202121822504.3U CN215757620U (en) | 2021-08-05 | 2021-08-05 | Corrosion device of germanium sheet or germanium spindle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202121822504.3U CN215757620U (en) | 2021-08-05 | 2021-08-05 | Corrosion device of germanium sheet or germanium spindle |
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| CN215757620U true CN215757620U (en) | 2022-02-08 |
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| CN202121822504.3U Active CN215757620U (en) | 2021-08-05 | 2021-08-05 | Corrosion device of germanium sheet or germanium spindle |
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