CN115763220A - Substrate processing method and semiconductor device manufacturing method - Google Patents
Substrate processing method and semiconductor device manufacturing method Download PDFInfo
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- CN115763220A CN115763220A CN202211339354.XA CN202211339354A CN115763220A CN 115763220 A CN115763220 A CN 115763220A CN 202211339354 A CN202211339354 A CN 202211339354A CN 115763220 A CN115763220 A CN 115763220A
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Abstract
The invention provides a substrate processing method and a semiconductor device manufacturing method. According to the invention, before the crystal bar is cut, the side surface of the crystal bar is firstly subjected to surface treatment by using a surface treatment agent, so that the crystal bar reacts with the surface treatment agent in the subsequent annealing process to form a modified layer, the crystal bar after the surface treatment is cut to obtain a plurality of substrates, the edge part of the outer ring of each substrate comprises a modified region, and due to the difference between the crystal lattices and the thermodynamic properties of materials in the modified region and the middle region of the substrate, a stable stress region is formed in the range of the modified region of the substrate, the direction and the degree of the distortion/bending of the substrate are controlled, the surface type of the substrate is further optimized, and the processing quality and the quality of the substrate are improved.
Description
Technical Field
The present invention relates to the field of semiconductor manufacturing technologies, and in particular, to a substrate processing method and a semiconductor device manufacturing method.
Background
In the manufacturing process of semiconductor devices, it is generally necessary to perform the growth of an epitaxial layer by means of a growth substrate for which substrate warpage/bowing is the most important factor affecting epitaxial uniformity. In the prior art, the crystal growth lump can reach over 100kg generally, the size is large, and the temperature field uniformity in the crystal growth process is not high, so that the crystal has large thermal stress. The bar drawing is to draw out crystal bars with various diameters from the crystal lump, and huge mechanical stress is generated around the crystal bars due to mechanical processing. Due to the existence of thermal stress and mechanical stress and random uncontrollable, the stress of the finally processed substrate is not uniform, and the substrate is twisted/bent, so that the substrate presents an asymmetric surface type, and the wavelength convergence of the subsequently formed epitaxial layer is reduced due to the asymmetric surface type substrate. The uniformity of the epitaxial layer wavelength directly affects the yield of the devices at the later stage.
In view of the above problems, it is necessary to provide a substrate processing method to improve the processing quality and quality of the substrate.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a substrate processing method and a semiconductor device manufacturing method. Before cutting the crystal bar, firstly, the surface treatment agent is utilized to carry out surface treatment on the side surface of the crystal bar, so that the crystal bar reacts with the surface treatment agent in the subsequent annealing process to form a modified layer, the crystal bar after the surface treatment is cut to obtain a plurality of substrates, the edge part of the outer ring of each substrate comprises a modified region, and due to the difference between the crystal lattice and the thermodynamic property of the materials in the middle regions of the modified region and the substrates, the range of the modified region of the substrate can form a stable stress region, so that the distortion/bending direction and degree of the substrate can be controlled, the surface type of the substrate is optimized, and the processing quality and quality of the substrate are improved.
To achieve the above and other related objects, an embodiment of the present invention provides a substrate processing method including the steps of:
carrying out surface treatment on the side surface of the crystal bar formed by the crystal growth by using a surface treatment agent;
annealing the surface-treated crystal bar to enable the side surface of the crystal bar to react with the surface treatment agent so as to form a modified layer on the side surface of the crystal bar;
and cutting the crystal bar to obtain a plurality of substrates, wherein the outer ring edge part of each substrate comprises a modified region.
Optionally, the surface treatment of the ingot comprises:
coating a surface treatment agent on the side surface of the crystal bar, and baking the crystal bar at the temperature of 100-200 ℃ for 0-2 h.
Optionally, the side surface of the crystal bar is coated with a surface treatment agent in an amount of 0.1mg/cm 2 ~100mg/cm 2 。
Optionally, before the surface treatment of the ingot, the method further includes the following steps:
providing a modifier, a catalyst, a dispersant and a solvent;
and uniformly mixing the modifier, the catalyst, the dispersant and the solvent to obtain the surface treating agent.
Optionally, annealing the surface-treated ingot further comprises the following steps:
putting the crystal bar coated with the surface treatment agent into a heating furnace;
annealing the crystal bar within the temperature range of 30-3000 ℃ for 0.1 h-30 days.
Optionally, annealing the surface-treated ingot further comprises:
and (3) heating: heating the heating furnace to 100-2000 ℃ at a heating rate of 0.5-200 ℃/min;
preserving heat: keeping the temperature for 0.1 to 500 hours at the temperature of between 100 and 2000 ℃;
cooling: and cooling the heating furnace to room temperature at a cooling rate of 0.5-200 ℃/min.
Optionally, the modified layer formed on the side surface of the crystal bar has a depth greater than 0 and less than 2mm.
Optionally, the modified region of the substrate is a circular ring extending inward from the edge of the outer ring of the substrate with the center of the substrate as a circle center, and a difference between an outer diameter and an inner diameter of the circular ring is greater than 0 and less than 200 μm.
Optionally, grinding the substrate obtained by cutting;
and annealing, chamfering and polishing the ground substrate.
Optionally, the extent of the substrate chamfer is greater than 200 μm.
A method for manufacturing a semiconductor device, comprising the steps of:
providing a substrate, wherein the substrate is obtained by the substrate processing method;
forming at least one semiconductor layer on the first surface or the second surface of the substrate;
and etching the semiconductor layer.
Optionally, the forming at least one semiconductor layer on the first surface or the second surface of the substrate further comprises:
forming a first semiconductor layer on the substrate;
forming an active layer over the first semiconductor layer;
forming a second semiconductor layer over the active layer, the second semiconductor layer having an opposite conductivity to the first semiconductor layer.
Optionally, the semiconductor device manufacturing method further includes forming a first electrode and a second electrode in communication with the first semiconductor layer and the second semiconductor layer, respectively.
As described above, the substrate processing method and the semiconductor device manufacturing method according to the present invention have at least the following advantageous effects: in the method, firstly, the side surface of a crystal bar is subjected to surface treatment by using a surface treatment agent, so that the crystal bar reacts with the surface treatment agent in the subsequent annealing process to form a modified layer, the crystal bar subjected to surface treatment is cut to obtain a plurality of substrates, the edge part of the outer ring of each substrate comprises a modified region, and due to the difference between the crystal lattices and the thermodynamic properties of materials in the middle regions of the modified region and the substrates, the thermal expansion coefficient of the modified region is different from that of the material in the middle region of the substrate, the modified region can generate consistent stress in the cooling process to ensure that the substrates form convergent and controllable distortion/bending, and the distortion/bending directions and degrees of the substrates tend to be the same, so that the surface types of the substrates tend to be consistent, the processing quality and quality of the substrates can be improved, in addition, the modified region can be turned into a surface width in the subsequent chamfering process, and the electrical parameters in the subsequent epitaxial process cannot be negatively influenced.
The semiconductor device of the invention adopts the method to process the substrate, thus compared with the semiconductor device obtained by processing the conventional substrate, the divergence of the wavelength of the epitaxial layer is reduced, the wavelength of the epitaxial layer is more convergent, and the yield of the semiconductor device is greatly improved.
Drawings
Fig. 1 shows a process flow diagram of a conventional substrate.
FIG. 2 is a flow chart illustrating the processing of a substrate according to one embodiment of the present invention.
FIG. 3 is a schematic side view of a crystal boule according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the form, quantity, position relationship and proportion of the components in actual implementation can be changed freely on the premise of implementing the technical solution of the present invention, and the layout form of the components may be more complicated. Thus, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the exemplary embodiments should not be considered limited to the specific shapes of the regions illustrated in the drawings, but may also include deviations in shapes that result, for example, from manufacturing processes. In the drawings, the length and size of some layers and regions may be exaggerated for clarity. Like reference numerals in the drawings denote like parts. It will also be understood that when a layer is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present.
The preparation of the substrate is a very important link in the manufacturing process of the semiconductor device, and the yield of the substrate directly influences the performance of the device. As shown in fig. 1, it is a process flow diagram of a conventional substrate, the substrate is generally a thin slice obtained by warp cutting a crystal bar formed by crystal growth, in the prior art, the crystal growth lump can reach over 100kg, the size is large, and the uniformity of temperature field in the crystal growth process is not high, which results in large thermal stress of the crystal. The bar drawing is to draw out crystal bars with various diameters from the crystal lump, and huge mechanical stress is generated around the crystal bars due to mechanical processing. Due to the existence of thermal stress and mechanical stress and random uncontrollable, the stress of the finally processed substrate is not uniform, and the substrate is twisted/bent, so that the substrate presents an asymmetric surface type, and the wavelength convergence of the subsequently formed epitaxial layer is reduced due to the asymmetric surface type substrate. The uniformity of the wavelength of the epitaxial layer directly affects the yield of the devices at the later stage. The invention provides a substrate processing method and a semiconductor device manufacturing method.
As shown in fig. 2, the processing flow of the substrate in this embodiment is illustrated, and in this embodiment, the ingot may be any crystal used in the manufacture of semiconductor devices, such as glass, compound semiconductors, metals and alloys, oxides, nitrides, group iii-v compounds, group iv simple substances and compounds, halides, silicates, carbonates, and the like. The crystal rod selected in the embodiment is a sapphire crystal rod, and the crystal growth process of the sapphire crystal rod is generally that firstly, a raw material of aluminum oxide is placed in a crucible, the crucible and the aluminum oxide in the crucible are heated to a temperature of more than 2000 ℃, so that the aluminum oxide is melted into a melt in a molten state; then seeding is carried out, the temperature of the liquid level of the melt is stabilized between 2050 ℃ and 2060 ℃, sapphire seed crystals are placed from the right upper part of the liquid level, and the seed crystals are contacted with the liquid level of the melt; then, shouldering: slowly pulling the seed crystal, uniformly increasing the weight of the crystal, and increasing the diameter of the crystal to a preset diameter; and (3) isometric growth: pulling the crystal at a constant speed and allowing the crystal to grow with equal diameters; cutting off: the diameter of the crystal is reduced until a sharp point is formed and the crystal is completely separated from the solution, and the temperature of the crystal after the crystal is separated from the solution is reduced, so that the sapphire crystal is obtained.
The utilization is drawn excellent machine and high-speed rotatory excellent cutter of drawing is drawn excellent along being on a parallel with sapphire crystal and is drawn excellent face direction and draw the stick to sapphire crystal, obtains sapphire crystal bar, and because thermal stress and mechanical stress's existence in the course of working of sapphire crystal bar this moment can make the substrate defect density that the direct processing obtained increase, and the warpage is great.
Therefore, as shown in fig. 3, a surface treatment agent is coated on the side surface 1 of the sapphire ingot to perform a surface treatment on the sapphire ingot. In this embodiment, the surface treatment agent includes a modifier: aluminate, silicate, carbonate, hydroxide, oxide, halide, or the like, catalyst: reducing materials (low-valent compounds such as carbon, silicon, sulfides, simple metal substances, iodides, ferrous salts and the like), oxidizing materials (high-valent compounds such as potassium permanganate, dichromate, chlorate, nitrate, ferric salt, cupric salt and the like), acid, alkali or ion salts, dispersing agents: at least one of castor oil, triolein and phosphate, solvent: various solvents such as alcohols, ketones, toluenes, ethers, esters, etc., and also mixed solvents of 1 or 2 kinds of alcohols and ketones or toluene. The modifier, the catalyst, the dispersant and the solvent are uniformly mixed and then coated on the surface of the substrate, and the thickness and the concentration of the surface treatment agent can be determined according to the depth of surface treatment on the sapphire crystal bar. In this example, the thickness of the surface treatment agent was more than 0.1mm, and the coating amount of the surface treatment agent was 0.1mg/cm 2 ~100mg/cm 2 。
After the side surface of the sapphire ingot is coated with the surface treatment agent, the sapphire ingot is baked, for example, at a temperature ranging from 100 ℃ to 200 ℃ for 0 to 2 hours. During this baking process, the surface treatment agent hardly reacts with the substrate, or reacts to a very small extent. But in the process, the surface treatment agent is primarily dried, so that the surface treatment agent and the sapphire crystal bar can be tightly attached together, and the surface treatment agent is convenient to react with the sapphire crystal bar in the subsequent annealing process.
After the surface treatment, the sapphire crystal bar with the surface treatment agent is placed into a heating furnace for annealing. In this embodiment, the annealing temperature is 30 ℃ to 3000 ℃ and the annealing time is about 0.1 hour to 30 days.
In an alternative embodiment, the annealing process consists essentially of: a heating stage, in which the heating furnace is heated to 100-2000 ℃ at a heating rate of 0.5-200 ℃/min. And (3) a heat preservation stage: keeping the temperature for 0.1 to 500 hours at the temperature of between 100 and 2000 ℃; and (3) cooling: cooling at the cooling rate of 0.5-200 ℃/min until the heating furnace is cooled to the room temperature. In a more preferable embodiment, the heating furnace is heated to 1300-1800 ℃ at a heating rate of 1-20 ℃/min, the temperature is kept at 1300-1800 ℃ for 1-100 hours, and then the temperature is reduced to room temperature at a cooling rate of 1-20 ℃/min.
In the heat preservation stage, the surface treatment agent and the sapphire crystal bar fully react. In the embodiment, the surface treating agent takes a calcium acetate ethanol solution as an example, and in the temperature rising stage, the calcium acetate solution loses all ethanol, and the calcium acetate is decomposed into acetone and calcium carbonate; in the high-temperature stage, the calcium carbonate undergoes decomposition:
CaCO 3 →CaO+CO 2 ↑
the reaction product CaO of the decomposition reaction has high reactivity and can react with the sapphire crystal bar at high temperature, and the reaction is as follows:
CaO+Al 2 O 3 →xCaO·yAl 2 O 3
in the above reaction formula, the values of x and y are both greater than zero, and different combinations of the values of x and y represent different reaction products, and a plurality of reaction products exist under the high temperature condition of the heat preservation stage described in this embodiment.
In the annealing process, a modifier in the surface treatment agent reacts from the surface of the side surface of the sapphire crystal bar under the action of a catalyst to form a modified layer, the modifier continuously diffuses towards the side surface of the sapphire crystal bar towards the inside along with the passage of time and gradually reacts, the thickness of the modified layer is continuously increased, the thickness of the modified layer can be controlled by controlling the heat preservation temperature and the heat preservation time, and the thickness of the modified layer can be controlled within the range of 0-200 mu m according to the requirement of the surface width in the subsequent chamfering process.
After the surface treatment and the annealing, a layer of material on the surface of the side surface of the sapphire crystal bar is modified, the crystal lattice and the thermodynamic property of the modified structure are different from those of sapphire, and the stress region in the modified region range is more stable compared with a sapphire substrate.
After the annealing is finished, performing wire cutting, grinding, annealing, chamfering, copper polishing and polishing on the sapphire ingot, wherein in the embodiment, the processes of wire cutting, grinding and the like are the same as the processing technology of the conventional sapphire substrate. In this embodiment, the width of the sapphire substrate chamfer is larger than 200 μm. In the processing method, the depth of the modified layer on the inner side of the side surface of the sapphire crystal bar is 0-200 μm, so that the sapphire substrate obtained after cutting the sapphire crystal bar has a modified area which is a circular ring from the edge part of the outer ring of the sapphire substrate to the center of the substrate, the difference between the outer diameter and the inner diameter of the circular ring is more than 0 and less than 200 μm, and in the chamfering process, the modified area is chamfered into a breadth area, so that the electrical parameters of the sapphire substrate in the subsequent epitaxial process cannot be influenced. The modified region is a structure obtained through high-temperature annealing, atoms in a modified material enter the surface of the sapphire in the annealing process to enable the atoms to be rearranged, and due to the difference of thermal expansion coefficients in the cooling process of the modified region, a relatively stable stress difference can be formed at the interface between the modified region and the middle region of the substrate.
Another embodiment of the present invention provides a semiconductor device manufacturing method, including the steps of:
the substrate is provided by the substrate processing method, and may be any substrate suitable for semiconductor production, for example, glass, compound semiconductors and insulators, metals and alloys, oxides, nitrides, iii-v compounds, ii-v compounds, fourth main group elements and compounds, halides, perovskite-type materials, silicates, carbonates, aluminates, and the like.
Forming at least one semiconductor layer on the first surface or the second surface of the substrate, in this embodiment, taking the example of forming a semiconductor layer on a sapphire substrate, the forming of the at least one semiconductor layer includes: a first semiconductor layer is first formed on a substrate, an active layer is then formed over the first semiconductor layer, and a second semiconductor layer is then formed over the active layer, the second semiconductor layer having a conductivity opposite to that of the first semiconductor layer. Also included are first and second electrodes formed in communication with the first and second semiconductor layers, respectively.
Etching the semiconductor layer, wherein the first semiconductor layer can be an N-type semiconductor layer, and the second semiconductor layer is a P-type semiconductor layer; the first semiconductor layer may be a P-type semiconductor layer, the second semiconductor layer may be an N-type semiconductor layer, and the active layer may be a multiple quantum well. And etching the at least one semiconductor layer to form a semiconductor light-emitting structure in the at least one semiconductor layer.
In the method for manufacturing a semiconductor device of the present invention, the substrate is processed by the substrate processing method of the present invention, so that the yield of the semiconductor device can be improved.
As described above, the substrate processing method and the semiconductor device manufacturing method according to the present invention have at least the following advantageous effects: according to the method, before the crystal bar is cut, the side face of the crystal bar is subjected to surface treatment by using a surface treatment agent, so that the crystal bar reacts with the surface treatment agent in the subsequent annealing process to form a modified layer, the crystal bar subjected to surface treatment is cut to obtain a plurality of substrates, the edge part of the outer ring of each substrate comprises a modified region, and due to the difference between the crystal lattice and the thermodynamic property of the material in the middle region of the modified region and the substrate, the thermal expansion coefficient of the modified region is different from that of the material in the middle region of the substrate, the modified region can generate stress in the cooling process, the stress is far greater than that of the middle region of the substrate, so that a relatively stable stress difference is formed at the interface between the modified region and the middle region of the substrate, the difference of the stress among a plurality of substrates can be converged, the twisting/bending directions and the degrees of the plurality of substrates tend to be the same, the surface type of the substrate is optimized, and the processing quality and the quality of the substrate are improved. The semiconductor device of the invention adopts the method to process the substrate, thus compared with the semiconductor device obtained by processing the conventional substrate, the divergence of the wavelength of the epitaxial layer is reduced, the wavelength of the epitaxial layer is more convergent, and the yield of the semiconductor device is greatly improved.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (13)
1. A substrate processing method is characterized in that,
the method comprises the following steps:
carrying out surface treatment on the side surface of the crystal bar formed by the crystal growth by using a surface treatment agent;
annealing the surface-treated crystal bar to enable the side surface of the crystal bar to react with the surface treatment agent so as to form a modified layer on the side surface of the crystal bar;
and cutting the crystal bar to obtain a plurality of substrates, wherein the outer ring edge part of each substrate comprises a modified region.
2. The method of processing a substrate according to claim 1, wherein the surface treatment of the ingot comprises:
coating a surface treatment agent on the side surface of the crystal bar, and baking the crystal bar at the temperature of 100-200 ℃ for 0-2 h.
3. The method as set forth in claim 2, wherein the surface treatment agent is coated on the side surface of the ingot in an amount of 0.1mg/cm 2 ~100mg/cm 2 。
4. The method of processing a substrate according to claim 1, further comprising, before the surface treatment of the ingot, the steps of:
providing a modifier, a catalyst, a dispersant and a solvent;
and uniformly mixing the modifier, the catalyst, the dispersant and the solvent to obtain the surface treating agent.
5. The method of processing a substrate according to claim 1, wherein annealing the surface-treated ingot further comprises:
putting the crystal bar coated with the surface treatment agent into a heating furnace;
annealing the crystal bar within the temperature range of 30-3000 ℃ for 0.1 h-30 days.
6. The method of claim 1, wherein annealing the surface treated ingot further comprises:
and (3) heating: heating the heating furnace to 100-2000 ℃ at a heating rate of 0.5-200 ℃/min;
and (3) heat preservation: keeping the temperature for 0.1 to 500 hours at the temperature of between 100 and 2000 ℃;
cooling: the heating furnace is cooled to the room temperature at the cooling rate of 0.5-200 ℃/min.
7. The method according to claim 1, wherein the modified layer formed on the side surface of the ingot has a depth of more than 0 mm and less than 2mm.
8. The method according to claim 1, wherein the modified region of the substrate is a ring extending inward from an outer edge of the substrate with a center of the substrate as a center, and a difference between an outer diameter and an inner diameter of the ring is greater than 0 and less than 200 μm.
9. A method of processing a substrate as recited in claim 1, further comprising the steps of: grinding the substrate obtained by cutting;
and annealing, chamfering and polishing the ground substrate.
10. A method of processing a substrate as recited in claim 9, wherein the substrate chamfer has a width greater than 200 μm.
11. A method for manufacturing a semiconductor device, comprising the steps of:
providing a substrate, wherein the substrate is obtained by the processing method of any one of claims 1 to 10;
forming at least one semiconductor layer on the first surface or the second surface of the substrate;
and etching the semiconductor layer.
12. The manufacturing method of a semiconductor device according to claim 11,
forming at least one semiconductor layer on the first surface or the second surface of the substrate further comprises:
forming a first semiconductor layer on the substrate;
forming an active layer over the first semiconductor layer;
forming a second semiconductor layer over the active layer having a conductivity opposite to that of the first semiconductor layer.
13. The manufacturing method of a semiconductor device according to claim 12, further comprising:
forming a first electrode and a second electrode in communication with the first semiconductor layer and the second semiconductor layer, respectively.
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