CN114231182A - Easy-to-cleave gallium oxide wafer chemical mechanical polishing process, polishing solution and preparation method thereof - Google Patents

Easy-to-cleave gallium oxide wafer chemical mechanical polishing process, polishing solution and preparation method thereof Download PDF

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Publication number
CN114231182A
CN114231182A CN202111633445.XA CN202111633445A CN114231182A CN 114231182 A CN114231182 A CN 114231182A CN 202111633445 A CN202111633445 A CN 202111633445A CN 114231182 A CN114231182 A CN 114231182A
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polishing
gallium oxide
surfactant
chemical mechanical
oxide wafer
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周海
蒋网
徐亚萌
任相璞
计健
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Yancheng Institute of Technology
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Yancheng Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00Lapping machines or devices; Accessories

Abstract

The invention discloses an easily-cleaved gallium oxide wafer chemical mechanical polishing process, polishing solution and a preparation method thereof. The abrasive is one or more of silicon dioxide, aluminum oxide, cerium oxide and diamond. The dispersant is a hydrophobically modified acrylic polymer. The oxidizing agent is hydrogen peroxide. The surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, amino acid type surfactant, and fatty alcohol-polyoxyethylene ether 5. The defoaming agent is tributyl phosphate. The pH regulator is a compound of inorganic base and organic base or inorganic acid and organic acid. The polishing process comprises the following steps: and (3) carrying out rough polishing, semi-fine polishing and fine polishing on the gallium oxide wafer in sequence by using independently developed polishing solution, wherein the polishing pad material is polyurethane. The invention improves the working efficiency and can ensure that the polished gallium oxide wafer has an ultra-smooth surface.

Description

Easy-to-cleave gallium oxide wafer chemical mechanical polishing process, polishing solution and preparation method thereof
Technical Field
The invention belongs to the technical field of ultra-precision machining of hard and brittle crystals, and particularly relates to an easily-cleaved gallium oxide wafer chemical mechanical polishing process, polishing solution and a preparation method thereof.
Background
Single crystal gallium oxide is a hard and brittle material, and as one of the new semiconductor materials, has attracted attention in recent years because of its series of excellent physicochemical properties, such as ultra-wide forbidden band, high breakdown field strength, excellent conductivity, high transmittance in deep ultraviolet band, and so on.
Chemical Mechanical Polishing (CMP), belonging to the ultra-precision machining regime, is a means of obtaining global planarization, the purpose of which is specifically designed to enable a surface to be obtained that is both flat and free of scratches and contamination by impurities. CMP is a technique combining mechanical action and chemical action, and a soft layer which is relatively easy to remove is generated by the chemical reaction of the surface material of a workpiece and additives such as an oxidant, a catalyst and the like in slurry, and then a polishing pad and abrasive particles are used for mechanical removal. The CMP technique can avoid surface damage caused by pure mechanical polishing and defects of low polishing speed, poor surface flatness and poor polishing consistency caused by single-purification chemical polishing, and can obtain an ultra-smooth surface with almost no damage.
The single crystal gallium oxide is mostly used as an optical material substrate, but due to the high hardness of gallium oxide, the easy generation of pits and scratches on the surface and the easy-to-understand property of gallium oxide, the processing is difficult, and the problems of low polishing efficiency, high surface roughness and material waste exist in the processing process, so that the application of gallium oxide is limited.
Disclosure of Invention
The invention discloses an easily-cleaved chemical mechanical polishing process for a gallium oxide wafer, polishing solution and a preparation method thereof, aiming at solving the problems of low polishing efficiency, high surface roughness and serious material waste of the existing gallium oxide wafer, and improving the polishing effect and reducing the surface roughness of the gallium oxide wafer.
The invention adopts the technical scheme that the easily-cleaved chemical mechanical polishing solution for the gallium oxide wafer comprises the components of an abrasive, a dispersing agent, an oxidizing agent, a surfactant, a defoaming agent and a pH regulator. The abrasive is one or more of silicon dioxide, aluminum oxide, cerium oxide and diamond. The dispersant is a hydrophobically modified acrylic polymer. The oxidizing agent is hydrogen peroxide. The surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, amino acid type surfactant, and fatty alcohol-polyoxyethylene ether 5. The defoaming agent is tributyl phosphate. The pH regulator is a compound of inorganic base and organic base or inorganic acid and organic acid.
The polishing process comprises the following steps: roughly polishing, semi-finely polishing and finely polishing the gallium oxide wafer in turn by using independently developed polishing solution, wherein the polishing pad material is polyurethane, the rotation speed of a polishing disc is 30-50r/min, the polishing pressure is 90-110g/cm2, the flow rate of the polishing solution is 1.8-2.0ml/min, and the polishing time is 90 min. The (100) crystal face and the (010) crystal face of the gallium oxide after the fine polishing reach ultra-smooth surfaces, and the surface roughness Ra of the gallium oxide can reach 6nm and 5nm (the measurement range is 145 multiplied by 100 mu m) respectively by measuring a VK topographer. The invention obtains the ultra-smooth and nondestructive processing surface of the easy-to-cleave gallium oxide wafer.
As a preferable scheme, the abrasive is one or more of silicon dioxide, aluminum oxide, cerium oxide and diamond, the average grain diameter of the abrasive grains is 20-100nm, and the mass fraction of the abrasive grains is 3-5% of the polishing solution. If the particle size of the abrasive grains is too large, scratches are likely to be generated on the surface of the workpiece, and if the particle size of the abrasive grains is too small, the removal efficiency is lowered. Too high abrasive concentration can lead to uneven dispersion of the abrasive and material waste, and too low concentration can reduce the number of scratches with a workpiece in unit time and lead to reduction of material removal rate. The particle size of the abrasive particles is 20-100nm, the abrasive particle concentration is 3-5%, and the polishing effect is optimal.
Preferably, the dispersant is a hydrophobically modified acrylic polymer, so that abrasive particles can be uniformly dispersed in the polishing solution, and the mass fraction of the dispersant is 0.05-1% of the polishing solution. The concentration of the dispersing agent is 0.05-1% and the polishing effect is best.
Preferably, the oxidizing agent is hydrogen peroxide, the mass fraction of the oxidizing agent is 0.01-0.04% of the polishing solution, and the oxidizing agent can enable the surface to be polished to generate a thin and loose oxide film which is easy to mechanically remove. Too low an oxidizer concentration may result in insufficient thickness of the oxide layer, thereby affecting the substrate surface polishing quality, and too high an oxidizer concentration may result in increased thickness of the oxide layer, thereby reducing material removal rate. The concentration of the oxidizing agent is empirically determined to be 0.01-0.04%, and the polishing effect is optimal.
As a preferable scheme, the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, amino acid type surfactant and fatty alcohol-polyoxyethylene ether 5, and the mass fraction of the surfactant is 0.1-0.5% of the polishing solution. Gallium oxide is amphoteric oxide, the surfactant plays an important role in the chemical mechanical polishing process of gallium oxide, the surface tension of the solution can be obviously reduced, polishing solution system abrasive particles are dispersed to a certain extent, and the surface of the substrate can be fully wetted. The mass fraction of the surface active agent is determined to be 0.1-0.5% of the polishing solution through experience, and the polishing effect is optimal.
Preferably, the defoaming agent is tributyl phosphate, the mass fraction of the defoaming agent is 0.01-2% of the polishing solution, and the defoaming agent is used for reducing the surface tension of the polishing solution and preventing and reducing foams. The concentration of the defoaming agent is determined by experience to be 0.01-2%, and the polishing effect is optimal.
As a preferable scheme, the pH regulator is a compound of an inorganic base and an organic base or an inorganic acid and an organic acid, and the mass ratio is 1: 15-20 parts of; the inorganic base is sodium hydroxide, the organic base is triethylamine, the inorganic acid is phosphoric acid, and the organic acid is citric acid. And adjusting the pH of the polishing solution to 10-12. Since acidic polishing solutions tend to corrode equipment and cause environmental pollution, alkaline polishing solutions are selected here. The pH value of the polishing solution is determined by experience to be 10-12, and the polishing effect is optimal.
The types of polishing pads commonly used at present mainly include polyurethane and non-woven fabric. The polyurethane polishing pad has high hardness and small deformation in the polishing process, and can easily obtain good surface precision. The surface of the non-woven fabric polishing pad has a fine villus structure, so that the non-woven fabric polishing pad can be more easily attached to the surface of a workpiece in the polishing process, the roughness obtained by polishing is lower, but the obtained surface type precision is inferior to that of a polyurethane polishing pad. Polyurethane materials are therefore selected here as polishing pads. The reasonable selection of the polishing process parameters has an important influence on the polishing effect of the gallium oxide substrate. As the polishing pressure increases, the mechanical interaction of the gallium oxide substrate with the polishing pad increases and the material removal rate increases. However, too high polishing pressure can prevent the polishing solution from entering the gap between the gallium oxide substrate and the polishing pad, which results in reduced chemical action and thinning of the gallium oxide surface reaction layer, resulting in reduced material removal rate. Since it is not desirable to use a large polishing pressure immediately before and immediately after polishing, the polishing pressure is applied in a load-hold-unload mode, and the pressure should be kept constant during polishing. As the rotation speed of the polishing disk is increased, the scribing times of the abrasive particles and the gallium oxide substrate are increased, and the material removal rate is also increased. However, too high a rotational speed may cause the slurry to be thrown off the surface of the polishing pad, which not only causes the slurry to be wasted, but also reduces the material removal rate. Therefore, the rotating speed of the polishing disk is 30-50r/min, the polishing pressure is 90-110g/cm2, the flow rate of the polishing solution is 1.8-2.0ml/min, and the polishing time is 90 min.
The invention has the beneficial effects that:
by adopting the easily-cleaved gallium oxide wafer chemical mechanical polishing process, the polishing solution and the preparation method thereof, the working efficiency is improved, the polished gallium oxide wafer can reach an ultra-smooth surface, and the surface roughness Ra of a (100) crystal face and a (010) crystal face of gallium oxide can respectively reach 6nm and 5nm (the measurement area is 145 multiplied by 100 mu m) observed by a VK (voltage K) topographer.
Drawings
FIG. 1 is a flow chart of a process for chemical mechanical polishing a disposable gallium oxide wafer according to the present invention;
FIG. 2 is a schematic representation of the crystal plane of a gallium oxide substrate (100) before polishing and its surface roughness measured with a VK topographer;
FIG. 3 is a schematic representation of the pre-polishing gallium oxide substrate (010) crystal plane and its surface roughness measured with a VK topographer;
FIG. 4 is a schematic diagram of the crystal plane of the roughly polished gallium oxide substrate (100) and its surface roughness measured by a VK topographer;
FIG. 5 is a schematic diagram of the crystal plane of the roughly polished gallium oxide substrate (010) and its surface roughness measured with a VK topographer;
FIG. 6 is a schematic diagram of the crystal plane and surface roughness of a semi-polished gallium oxide substrate (100) measured by a VK topographer;
FIG. 7 is a schematic diagram of the crystal plane of the semi-polished gallium oxide substrate (010) and its surface roughness measured with a VK topographer;
FIG. 8 is a schematic diagram of the crystal plane of the gallium oxide substrate (100) after finish polishing and its surface roughness measured by VK topographer;
FIG. 9 is a schematic diagram of the crystal plane of the gallium oxide substrate (010) after finish polishing and its surface roughness measured with a VK topographer.
Detailed Description
For the purposes of promoting an understanding and understanding of the invention, reference will now be made to the following descriptions taken in conjunction with the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended claims.
FIG. 2 shows the results of measuring the surface roughness of the (100) crystal plane and the (010) crystal plane of the gallium oxide substrate before polishing with a VK topographer, for a gallium oxide (100) wafer as a polishing sample and a gallium oxide (010) wafer as a polishing sample, and the measured area is 145X 100. mu.m. The results showed that the Ra value of the surface roughness of gallium oxide (100) crystal plane before polishing was 18nm, and the Ra value of the surface roughness of (010) crystal plane was 16 nm. And (3) adhering the polished sample on a circular glass slide disc by using paraffin, wherein the length, the width and the height of the sample are respectively 10mm, 10mm and 1 mm. The polishing pressure is adjusted by changing the mass of the weight on the slide plate. The processing equipment is a rotary swinging gravity type grinding and polishing machine.
And preparing the abrasive, the dispersing agent, the oxidizing agent, the surfactant, the defoaming agent, the pH regulator and the deionized water into polishing solution for chemical mechanical polishing of the gallium oxide wafer. The polishing pad material is polyurethane, wherein the abrasive is silicon dioxide, the dispersing agent is a hydrophobic modified acrylic polymer, the oxidant is hydrogen peroxide, the surfactant is cetyl trimethyl ammonium bromide, the defoaming agent is tributyl phosphate, the pH regulator is a compound of inorganic base and organic base.
The polishing equipment is a ZYP230 rotary oscillating gravity type grinding and polishing machine produced by Shenyang wheat crystal material processing equipment. Setting polishing process parameters: the rotation speed is 30-50r/min, the pressure is 90-110g/cm2, the flow rate of the polishing solution is 1.8-2.0ml/min, and the polishing time is 90 min.
The surface roughness of the gallium oxide wafers was measured before and after polishing with a VK topographer over a measurement range of 145X 100. mu.m. The mass of the gallium oxide wafer before and after polishing was measured by an electronic balance, and the material removal rate thereof was calculated.
The whole polishing process is shown in fig. 1 and comprises the following steps:
the rough polishing process:
polishing solution: the particle size of the silicon dioxide is 100nm, the content of the silicon dioxide is 4%, the dispersing agent is a hydrophobic modified acrylic polymer, the content of the dispersing agent is 0.5%, the oxidant is hydrogen peroxide, the content of the oxidizing agent is 0.02%, the surfactant is cetyl trimethyl ammonium bromide, the content of the surfactant is 0.3%, the defoaming agent is tributyl phosphate, the content of the defoaming agent is 0.05%, the pH regulator is potassium hydroxide, and the pH value is 12.
And (3) polishing: the rotation speed of the polishing disc is 50r/min, the polishing pressure is 110g/cm2, the flow rate of the polishing solution is 2.0ml/min, and the polishing time is 90 min.
As shown in attached figures 4 and 5, the surface roughness Ra of the (100) crystal face and the (010) crystal face of the roughly polished gallium oxide is 15nm and 13nm respectively, and the MRR is 5980nm/h and 5750nm/h respectively.
Semi-fine polishing process:
polishing solution: the particle size of the silicon dioxide is 50nm, the content of the silicon dioxide is 4%, the dispersing agent is a hydrophobic modified acrylic polymer, the content of the dispersing agent is 0.5%, the oxidant is hydrogen peroxide, the content of the oxidizing agent is 0.02%, the surfactant is cetyl trimethyl ammonium bromide, the content of the surfactant is 0.3%, the defoaming agent is tributyl phosphate, the content of the defoaming agent is 0.05%, the pH regulator is potassium hydroxide, and the pH value is 11.
And (3) polishing: the rotation speed of the polishing disc is 40r/min, the polishing pressure is 100g/cm2, the flow rate of the polishing solution is 1.9ml/min, and the polishing time is 90 min.
As shown in the attached figures 6 and 7, the surface roughness Ra of the (100) crystal face and the (010) crystal face of the gallium oxide after semi-finish polishing is respectively 9nm and 7nm, and the MRR is respectively 2790nm/h and 2630 nm/h.
And (3) fine polishing process:
polishing solution: the particle size of the silicon dioxide is 20nm, the content of the silicon dioxide is 4%, the dispersing agent is a hydrophobic modified acrylic polymer, the content of the dispersing agent is 0.5%, the oxidant is hydrogen peroxide, the content of the oxidizing agent is 0.02%, the surfactant is cetyl trimethyl ammonium bromide, the content of the surfactant is 0.3%, the defoaming agent is tributyl phosphate, the content of the defoaming agent is 0.05%, the pH regulator is potassium hydroxide, and the pH value is 10.
And (3) polishing: the rotation speed of the polishing disc is 30r/min, the polishing pressure is 90g/cm2, the flow rate of the polishing solution is 1.8ml/min, and the polishing time is 90 min.
As shown in the attached figures 8 and 9, the surface roughness Ra of the (100) crystal face and the (010) crystal face of the gallium oxide after the fine polishing is respectively 6nm and 5nm, and the MRR is respectively 1490nm/h and 1380 nm/h.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the foregoing embodiments are merely illustrative of the technical spirit and features of the present invention, and the present invention is not limited thereto but may be implemented by those skilled in the art.

Claims (12)

1. An easy-to-cleave chemical mechanical polishing solution for gallium oxide wafers is characterized in that: the composite material comprises the following components in percentage by mass: 3-5% of abrasive particles, 0.05-0.1% of dispersing agent, 0.1-0.5% of surfactant, 0.01-0.04% of oxidant, 0.01-2% of defoaming agent, 1-5% of pH regulator and the balance of deionized water.
2. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the abrasive particles are at least one of: silicon dioxide, aluminum oxide, cerium oxide, diamond.
3. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the average grain diameter of the abrasive grains is 20-100 nm.
4. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the surfactant is at least one of the following: cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants.
5. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 4, characterized by: the cationic surfactant is cetyl trimethyl ammonium bromide; the anionic surfactant is sodium dodecyl benzene sulfonate; the zwitterionic surfactant is an amino acid type surfactant; the nonionic surfactant is fatty alcohol-polyoxyethylene ether 5.
6. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the dispersant is a hydrophobically modified acrylic polymer.
7. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the oxidant is hydrogen peroxide.
8. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the defoaming agent is tributyl phosphate.
9. The easy-to-understand gallium oxide wafer chemical mechanical polishing solution of claim 1, characterized by: the pH regulator is inorganic base and organic base or a compound of inorganic acid and organic acid, and the mass ratio is 1: 15-1: 20; the inorganic base is sodium hydroxide, the organic base is triethylamine, the inorganic acid is phosphoric acid, and the organic acid is citric acid.
10. A preparation method of easy-to-understand gallium oxide wafer chemical mechanical polishing solution is characterized in that: the method comprises the following steps:
s1, preparing abrasive particle suspension: weighing abrasive particles according to the mass ratio, preparing an abrasive particle suspension, and continuously stirring;
s2, adding a dispersing agent: weighing a dispersing agent according to the mass ratio, adding the dispersing agent into the abrasive particle suspension in the step (1), and continuously stirring;
s3, adding an oxidizing agent: weighing an oxidant according to the mass ratio, dissolving the oxidant in deionized water, and continuously stirring;
s4, dissolving the surfactant: weighing the surfactant according to the mass ratio, dissolving the surfactant in deionized water, and continuously stirring to completely dissolve the surfactant;
s5, mixing: mixing the solutions obtained in the steps S2, S3 and S4, and continuously stirring;
s6, adding a defoaming agent: weighing a defoaming agent according to the mass ratio, adding the defoaming agent into the mixed solution obtained in the step (5), and uniformly stirring;
s7, adding a pH regulator: and (4) adjusting the pH of the solution obtained in the step (6) to 10-12 by using a pH regulator to obtain the polishing solution for gallium oxide chemical mechanical polishing.
11. An easily-cleaved gallium oxide wafer chemical mechanical polishing process is characterized in that: the method comprises the following steps:
t1, preparing abrasive particle suspension with a certain concentration, adding a dispersing agent into the abrasive particle suspension, dissolving an oxidant in deionized water, dissolving a surfactant in the deionized water, mixing the surfactant, the dispersant and the deionized water, adding a defoaming agent and a pH regulator, and finally obtaining the polishing solution for chemically-mechanically polishing the easily-cleaved gallium oxide wafer;
t2, roughly polishing the gallium oxide wafer by using the prepared polishing solution, wherein the polishing pad material is polyurethane, the average grain diameter of the polishing solution is 100nm, the rotating speed of a polishing disc is 50r/min, and the polishing pressure is 110g/cm2The flow rate of the polishing solution is 2.0ml/min, and the polishing time is 90 min;
t3, step pairSemi-fine polishing is carried out on the gallium oxide wafer after the rough polishing in the step T2, the polishing pad material is polyurethane, the average grain diameter of the polishing solution is 50nm, the rotating speed of a polishing disc is 40r/min, and the polishing pressure is 100g/cm2The flow rate of the polishing solution is 1.9ml/min, and the polishing time is 90 min;
t4, finely polishing the gallium oxide wafer after the semi-fine polishing in the step T3, wherein the polishing pad material is polyurethane, the average grain size of the polishing solution is 20nm, the rotating speed of a polishing disc is 30r/min, and the polishing pressure is 90g/cm2The flow rate of the polishing solution was 1.8ml/min, and the polishing time was 90 min.
12. A process of chemical mechanical polishing of a disposable gallium oxide wafer according to claim 11, characterized by: the gallium oxide wafer after the fine polishing is an ultra-smooth surface, the measurement range is 145 multiplied by 100 mu m, and the surface roughness Ra of the gallium oxide (100) crystal face and the surface roughness Ra of the gallium oxide (010) crystal face measured by a VK topography instrument are 6nm and 5nm respectively.
CN202111633445.XA 2021-12-29 2021-12-29 Easy-to-cleave gallium oxide wafer chemical mechanical polishing process, polishing solution and preparation method thereof Pending CN114231182A (en)

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