CN117304814B - Polycrystalline silicon carbide substrate polishing agent, polishing method and polycrystalline silicon carbide substrate - Google Patents

Polycrystalline silicon carbide substrate polishing agent, polishing method and polycrystalline silicon carbide substrate Download PDF

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Publication number
CN117304814B
CN117304814B CN202311610879.7A CN202311610879A CN117304814B CN 117304814 B CN117304814 B CN 117304814B CN 202311610879 A CN202311610879 A CN 202311610879A CN 117304814 B CN117304814 B CN 117304814B
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silicon carbide
polycrystalline silicon
abrasive
carbide substrate
polishing
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CN117304814A (en
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郭超
母文凤
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Jc Innovative Semiconductor Substrate Technology Co ltd
Beijing Qinghe Jingyuan Semiconductor Technology Co ltd
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Jc Innovative Semiconductor Substrate Technology Co ltd
Beijing Qinghe Jingyuan Semiconductor Technology Co ltd
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    • 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
    • B24B1/00Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • 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
    • B24B37/04Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • 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
    • B24B37/04Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/07Lapping machines or devices; Accessories designed for working plane surfaces characterised by the movement of the work or lapping tool
    • B24B37/10Lapping machines or devices; Accessories designed for working plane surfaces characterised by the movement of the work or lapping tool for single side lapping
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/0445Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising crystalline silicon carbide
    • H01L21/0475Changing the shape of the semiconductor body, e.g. forming recesses

Abstract

The application relates to the technical field of semiconductor material processing, in particular to a polycrystalline silicon carbide substrate polishing agent, a polishing method and a polycrystalline silicon carbide substrate. The polishing agent comprises an oxidant, a dispersing agent, an abrasive a and an abrasive b; the hardness of the abrasive a is between the hardness of the oxide of the polycrystalline silicon carbide and the hardness of the polycrystalline silicon carbide body; the hardness of abrasive b is higher than that of the polycrystalline silicon carbide body. The polishing method comprises the following steps: A. selecting a polycrystalline silicon carbide substrate, wherein the maximum included angle of the crystal directions of different crystal grains of the polycrystalline silicon carbide substrate is smaller than 10 degrees; B. performing chemical mechanical polishing on the surface of the polycrystalline silicon carbide substrate, wherein the roughness of the surface of the polycrystalline silicon carbide substrate is less than 1nm; C. and B, scanning the surface of the polycrystalline silicon carbide substrate polished in the step B by using a plasma beam, and finishing the polishing of the polycrystalline silicon carbide substrate, wherein the surface roughness of the polycrystalline silicon carbide substrate is less than 0.5 nm. The surface roughness of the polished polycrystalline silicon carbide substrate can meet the requirement of a bonding process.

Description

Polycrystalline silicon carbide substrate polishing agent, polishing method and polycrystalline silicon carbide substrate
Technical Field
The application relates to the technical field of semiconductor material processing, in particular to a polycrystalline silicon carbide substrate polishing agent, a polishing method and a polycrystalline silicon carbide substrate.
Background
In order to solve the problems of low yield and high cost of monocrystalline silicon carbide substrates, composite structure substrates formed by bonding polycrystalline silicon carbide substrates and monocrystalline silicon carbide thin layers are being adopted in the industry. The polycrystalline silicon carbide substrate is used as a supporting layer of the composite structure substrate, and has lower resistivity and lower cost. Before bonding and connecting the polycrystalline silicon carbide substrate and the silicon carbide single crystal layer, the surface of the polycrystalline silicon carbide substrate needs to be processed to a roughness of 0.2nm or less.
Currently, polishing techniques for single crystal silicon carbide are mature, but polishing techniques for polycrystalline silicon carbide are lacking in research. The monocrystalline silicon carbide is generally oxidized by adopting a chemical mechanical polishing method and oxidizing agents such as potassium permanganate, hydrogen peroxide and the like, and is mechanically removed by adopting aluminum oxide, silicon oxide and cerium oxide as abrasive materials; because the hardness of the abrasive such as alumina, silica, and ceria is between that of the oxide of single crystal silicon carbide and that of the single crystal silicon carbide body, the abrasive can remove the oxide of single crystal silicon carbide without scratching the single crystal silicon carbide body, and thus a very flat surface free from surface scratches can be obtained.
The following problems exist in using existing chemical mechanical polishing techniques for single crystal silicon carbide directly for polishing polycrystalline silicon carbide: the grain orientation of polycrystalline silicon carbide is not uniform, and the rate at which grains of different orientations are oxidized by the oxidizing agent is different, resulting in a height difference between the grains. The surface roughness of the polycrystalline silicon carbide substrate processed by the existing chemical mechanical polishing technology is higher than 5nm, and the bonding requirement cannot be met.
Disclosure of Invention
The invention aims to provide a polishing agent for a polycrystalline silicon carbide substrate, which is used for polishing the polycrystalline silicon carbide substrate, and also provides a polishing method for the polycrystalline silicon carbide substrate, so that the polycrystalline silicon carbide substrate polished by the polishing agent or the polishing method can meet the bonding process requirement.
To achieve the purpose, the invention adopts the following technical scheme:
a polycrystalline silicon carbide substrate polishing agent comprising an oxidizing agent, a dispersing agent, an abrasive a and an abrasive b;
the hardness of the abrasive a is between the hardness of the oxide of the polycrystalline silicon carbide and the hardness of the polycrystalline silicon carbide body;
the hardness of the abrasive b is higher than that of the polycrystalline silicon carbide body.
Further, the oxidant comprises at least one of potassium permanganate, potassium nitrate, hydrogen peroxide, sodium hypochlorite and strong alkali;
the dispersing agent comprises at least one of sodium hexametaphosphate, sodium silicate, first amyl alcohol, fatty acid polyethylene glycol ester, polyacrylamide and sodium dodecyl sulfate.
Further, the abrasive a comprises at least one of alumina, silica, and ceria.
Further, the abrasive b includes diamond.
Further, the abrasive a and the abrasive b are particles;
the particle size of abrasive b is smaller than abrasive a.
Further, the particle size of the abrasive a is 30-200nm;
the particle size of the abrasive b is 5-30nm.
Further, the abrasive b ratio satisfies the following relationship:
g2/(g1+g2) =k×var, where k takes 0.5-2, var=2× (Omax-Omin)/(omax+omin);
var<5%;
wherein: g1 is the volume of the abrasive 1, G2 is the volume of the abrasive 2, omax is the maximum oxidation rate (mum/h) of the oxidizing agent to the grains with different crystal directions, omin is the minimum oxidation rate (mum/h) of the oxidizing agent to the grains with different crystal directions, and var is the oxidation rate difference rate.
A method of polishing a polycrystalline silicon carbide substrate comprising the steps of:
A. selecting a polycrystalline silicon carbide substrate, wherein the maximum included angle of the crystal directions of different crystal grains of the polycrystalline silicon carbide substrate is smaller than 10 degrees;
B. performing chemical mechanical polishing on the surface of the polycrystalline silicon carbide substrate, wherein the roughness of the surface of the polycrystalline silicon carbide substrate is less than 1nm; the polishing agent adopted by the chemical mechanical polishing is the polishing agent;
C. and B, scanning the surface of the polycrystalline silicon carbide substrate polished in the step B by using a plasma beam, and finishing the polishing of the polycrystalline silicon carbide substrate, wherein the surface roughness of the polycrystalline silicon carbide substrate is less than 0.5 nm.
Further, the plasma beam is focused by the plasma;
the plasma is obtained by ionization of gas;
the gas comprises at least one of oxygen, argon, helium, nitrogen, hydrogen and air;
the power of the radio frequency power supply for gas ionization is 200-1000W, and the gas flow is 50-200sccm.
The polycrystalline silicon carbide substrate is polished by the polishing agent or by the polishing method.
The invention has the beneficial effects that:
selecting a polycrystalline silicon carbide substrate with the maximum included angle of different crystal grains less than 10 degrees, wherein in the chemical mechanical polishing step, the abrasive comprises an abrasive 1 and an abrasive 2, and the realization is realized by reasonably configuring the proportion of the abrasive 2 and the grain size distribution of the abrasive 2 and the abrasive 1: the abrasive material can reduce or eliminate the height difference between grains caused by the oxidation rate difference of grains with different orientations, meanwhile, the abrasive material 2 has less scratches on the surface of the polycrystalline silicon carbide substrate, and the roughness of the processed surface is less than 1nm. On the basis of the above, the surface roughness of the polycrystalline silicon carbide substrate is reduced to 0.5nm by further polishing with plasma so as to meet the requirement of the polycrystalline silicon carbide substrate in the bonding process.
Drawings
FIG. 1 is a schematic diagram showing the height difference between grains caused by the difference of oxidation rates of grains in different orientations;
in the figure: 1. a polycrystalline silicon carbide substrate; 1-1, crystal grains; 2. an abrasive a; 3. and (3) grinding material b.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting thereof.
The invention provides a polycrystalline silicon carbide substrate polishing agent, which comprises an oxidant, a dispersing agent, an abrasive a and an abrasive b, wherein the hardness of the abrasive a is between that of an oxide of polycrystalline silicon carbide and that of a polycrystalline silicon carbide body, and the hardness of the abrasive b is higher than that of the polycrystalline silicon carbide body. The oxidant comprises at least one of potassium permanganate, potassium nitrate, hydrogen peroxide, sodium hypochlorite and strong alkali; the dispersant comprises at least one of sodium hexametaphosphate, sodium silicate, first amyl alcohol, fatty acid polyethylene glycol ester, polyacrylamide and sodium dodecyl sulfate. The abrasive a comprises at least one of alumina, silica and cerium oxide. The abrasive b comprises diamond. The abrasive a and the abrasive b are particles, the particle size of the abrasive a is 30-200nm, and the particle size of the abrasive b is 5-30nm; the particle size of abrasive b is smaller than abrasive a.
The abrasive b ratio satisfies the following relationship: g2/(g1+g2) =k×var, where k takes 0.5-2. Wherein: g1 is the volume of abrasive 1, G2 is the volume of abrasive 2, var is the oxidation rate differential rate.
If k is less than 0.5, namely the volume ratio of the abrasive b is too small, the abrasive can remove oxides on the polycrystalline silicon carbide substrate, but the removal effect on the polycrystalline silicon carbide substrate body is weak, the height difference among grains caused by the oxidation rate difference of grains with different orientations cannot be reduced, the height difference among the grains can always exist, and the surface roughness of the polycrystalline silicon carbide substrate is more than 1nm.
If k is more than 2, that is, the volume ratio of the abrasive b is too large, the abrasive not only can remove the oxide on the surface of the polycrystalline silicon carbide, but also has a strong effect of removing the polycrystalline silicon carbide body, and although the height difference between grains caused by the oxidation rate difference of grains with different orientations can be reduced or eliminated, the abrasive b (diamond) causes too many scratches on the surface of the polycrystalline silicon carbide substrate, the surface roughness of the substrate is reduced, and the surface roughness of the processed substrate is more than 1nm.
Under the condition that k is more than 0.5 and less than 2, the volume ratio of the abrasive material b is moderate, the abrasive material not only can reduce or eliminate the height difference among grains caused by the oxidation rate difference of grains with different orientations, but also has less scratch on the surface of the substrate caused by the abrasive material b (diamond), and the surface roughness of the processed substrate is less than 1nm.
Wherein: var=2× (Omax-Omin)/(omax+omin); var < 5%.
Wherein Omax is the maximum oxidation rate (μm/h) of the oxidizing agent to the crystal grains with different crystal directions, omin is the minimum oxidation rate (μm/h) of the oxidizing agent to the crystal grains with different crystal directions, the oxidation rates of the oxidizing agent to the crystal grains with different crystal directions are different, and the Omax value can be obtained through experiments.
Example 1
The present embodiment provides a polishing method of a polycrystalline silicon carbide substrate:
A. selecting a polycrystalline silicon carbide substrate, wherein the crystal form of the polycrystalline silicon carbide substrate is 3C, the surface of the polycrystalline silicon carbide substrate is mainly in a {110} crystal direction, and the maximum included angle of the crystal directions of different crystal grains is 9 degrees;
B. the polycrystalline silicon carbide substrate is subjected to chemical mechanical polishing. Wherein: the oxidant in the polishing agent is potassium permanganate, and the oxidation rate difference ratio var of different crystal grains is=3%; abrasive a is alumina, abrasive b is diamond, and the volume ratio of abrasive b is=2var=6%. The particle size range of the abrasive a is 30-200nm, and the particle size range of the abrasive b is 5-30nm. The polishing head pressed the polycrystalline silicon carbide substrate against the polishing disk at a pressure of 7psi, the polishing head rotational speed was 90rpm, and the polishing time was 20 minutes. The polishing agent supply amount was 300ml/min.
C. And (3) scanning the surface of the polycrystalline silicon carbide substrate polished in the step B by using a plasma beam. The plasma beam scans the surface of the polycrystalline silicon carbide substrate, reacts with the silicon carbide material, and removes the surface material of the slightly raised grains through the bombardment effect, so that the surface of the polycrystalline silicon carbide substrate is further smooth, and the polishing of the polycrystalline silicon carbide substrate is completed. Wherein: the plasma beam is focused by plasma, the plasma is obtained by ionization of gas, the gas is mixed gas of oxygen, hydrogen and argon, the power of a radio frequency power supply for gas ionization is 500W, and the total flow of the gas is 100sccm.
Example 2
A. Selecting a polycrystalline silicon carbide substrate, wherein the crystal form of the polycrystalline silicon carbide substrate is 3C, the surface of the polycrystalline silicon carbide substrate is mainly in a {110} crystal direction, and the maximum included angle of the crystal directions of different crystal grains is 4 degrees;
B. the polycrystalline silicon carbide substrate is subjected to chemical mechanical polishing. Wherein: the oxidant in the polishing agent is potassium permanganate, and the oxidation rate difference ratio var of different crystal grains is=2%; abrasive a is alumina, abrasive b is diamond, and the volume ratio of abrasive b=0.5var=1%. The particle size range of the abrasive a is 30-200nm, and the particle size range of the abrasive b is 5-30nm. The polishing head pressed the polycrystalline silicon carbide substrate against the polishing disk at a pressure of 7psi, the polishing head rotational speed was 90rpm, and the polishing time was 20 minutes. The polishing agent supply amount was 300ml/min.
C. And (3) scanning the surface of the polycrystalline silicon carbide substrate polished in the step B by using a plasma beam. The plasma beam scans the surface of the polycrystalline silicon carbide substrate, reacts with the silicon carbide material, and removes the surface material of the slightly raised grains through the bombardment effect, so that the surface of the polycrystalline silicon carbide substrate is further smooth, and the polishing of the polycrystalline silicon carbide substrate is completed. Wherein: the plasma beam is focused by plasma, the plasma is obtained by ionization of gas, the gas is mixed gas of oxygen, hydrogen and argon, the power of a radio frequency power supply for gas ionization is 500W, and the total flow of the gas is 100sccm.
Comparative example 1
The difference compared to example 1 is that the polycrystalline silicon carbide substrate is selected such that the maximum angle of the crystal orientation of the different grains is 12 °. Oxidation rate variance ratio var=7% for different grains. Abrasive b was 3.5%. The remaining conditions were the same.
Comparative example 2
The difference compared to example 1 is that the particle size distribution of abrasive b is in the range of 30-200nm. The remaining conditions were the same.
Comparative example 3
In comparison with example 1, k has a value of 0.3 and the proportion of abrasive b is 0.9%. The remaining conditions were the same.
Comparative example 4
In comparison with example 1, k has a value of 2.5 and the proportion of abrasive b is 7.5%. The remaining conditions were the same.
The roughness of the polysilicon carbide substrate polished by the examples and comparative examples is shown in the following table.
The embodiment and the comparative example show that the polishing agent and the polishing method provided by the invention have low surface roughness of the polished polycrystalline silicon carbide substrate, and can directly meet the bonding process requirement.
The embodiment also provides a polycrystalline silicon carbide substrate, wherein the maximum included angle of the crystal directions of different crystal grains is smaller than 10 degrees, and the surface roughness is smaller than 0.2nm after the polycrystalline silicon carbide substrate is polished by the polishing method in the embodiment 1 or 2, so that the bonding process requirement can be directly met.
It is to be understood that the above examples of the present invention are provided for clarity of illustration only and are not limiting of the embodiments of the present invention. Various obvious changes, rearrangements and substitutions can be made by those skilled in the art without departing from the scope of the invention. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (5)

1. The polycrystalline silicon carbide substrate polishing agent is characterized in that: comprises an oxidant, a dispersing agent, an abrasive a and an abrasive b;
the hardness of the abrasive a is between the hardness of the oxide of the polycrystalline silicon carbide and the hardness of the polycrystalline silicon carbide body;
the hardness of the abrasive b is higher than that of the polycrystalline silicon carbide body;
the abrasive a comprises at least one of alumina, silica and cerium oxide;
abrasive b comprises diamond;
the abrasive a and the abrasive b are particles;
the particle size of the abrasive a is 30-200nm;
the particle size of the abrasive b is 5-30nm;
the particle size of the abrasive b is smaller than that of the abrasive a;
the abrasive b ratio satisfies the following relationship:
g2/(g1+g2) =k×var, where k takes 0.5-2, var=2× (Omax-Omin)/(omax+omin);
var<5%;
wherein: g1 is the volume of the abrasive 1, G2 is the volume of the abrasive 2, omax is the maximum oxidation rate (mum/h) of the oxidizing agent to the grains with different crystal directions, omin is the minimum oxidation rate (mum/h) of the oxidizing agent to the grains with different crystal directions, and var is the oxidation rate difference rate;
the polishing agent is used for polishing polycrystalline silicon carbide substrates with different crystal grains and the maximum included angle of the crystal directions being less than 10 degrees.
2. The polishing agent according to claim 1, wherein: the oxidant comprises at least one of potassium permanganate, potassium nitrate, hydrogen peroxide, sodium hypochlorite and strong alkali;
the dispersing agent comprises at least one of sodium hexametaphosphate, sodium silicate, first amyl alcohol, fatty acid polyethylene glycol ester, polyacrylamide and sodium dodecyl sulfate.
3. A method of polishing a polycrystalline silicon carbide substrate, comprising the steps of:
A. selecting a polycrystalline silicon carbide substrate, wherein the maximum included angle of the crystal directions of different crystal grains of the polycrystalline silicon carbide substrate is smaller than 10 degrees;
B. performing chemical mechanical polishing on the surface of the polycrystalline silicon carbide substrate, wherein the roughness of the surface of the polycrystalline silicon carbide substrate is less than 1nm; the polishing agent used in the chemical mechanical polishing is the polishing agent according to any one of claims 1 to 2;
C. and B, scanning the surface of the polycrystalline silicon carbide substrate polished in the step B by using a plasma beam, and finishing the polishing of the polycrystalline silicon carbide substrate, wherein the surface roughness of the polycrystalline silicon carbide substrate is less than 0.5 nm.
4. A polishing method according to claim 3, wherein: the plasma beam is focused by plasma;
the plasma is obtained by ionization of gas;
the gas comprises at least one of oxygen, argon, helium, nitrogen, hydrogen and air;
the power of the radio frequency power supply for gas ionization is 200-1000W, and the gas flow is 50-200sccm.
5. A polycrystalline silicon carbide substrate characterized by: obtained by polishing with the polishing agent according to any one of claims 1 to 2 or by polishing with the polishing method according to any one of claims 3 to 4.
CN202311610879.7A 2023-11-29 2023-11-29 Polycrystalline silicon carbide substrate polishing agent, polishing method and polycrystalline silicon carbide substrate Active CN117304814B (en)

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