CN107785304B - SOI material with nitride film as insulating buried layer and preparation method thereof - Google Patents
SOI material with nitride film as insulating buried layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an SOI material with a nitride film as an insulating buried layer and a preparation method thereof, belonging to the technical field of semiconductor material manufacture. The nitride composite insulating film with good heat-conducting property and compact structure is prepared by utilizing a PECVD method, andthe SOI material is combined with the processes of hydrogen ion implantation, wafer bonding, annealing, grinding and polishing, microwave lobe-cracking and the like to prepare the SOI structure taking the silicon oxynitride/silicon nitride/silicon oxynitride composite film as the insulating layer, and the heat-conducting property of the SOI material is superior to that of the conventional SiO material2The SOI with the insulating buried layer is more suitable for the requirements of high-temperature and high-power SOI circuits. In addition, the dielectric constant of silicon nitride is larger than that of SiO2The dielectric constant of (2) can be used as a candidate material of a gate dielectric.
Description
Technical Field
The invention relates to the technical field of semiconductor material preparation, in particular to an SOI material taking a nitride film as an insulating buried layer and a preparation method thereof.
Background
Because of the unique superiority of SOI structure, the device based On this structure will essentially reduce junction capacitance and leakage current, increase switching speed, reduce power consumption, realize high speed and low power consumption operation, and its performance is obviously superior to bulk Silicon device and circuit. At present, the application of the SOI device is gradually expanded from military, aerospace and industry to the fields of data processing, communication, consumer electronics and the like. As a next-generation silicon-based integrated circuit technology, the SOI technology is widely applied to most of the fields of microelectronics, and also applied to other fields such as optoelectronics, MEMS, and the like. It is due to the above-mentioned advantages and wide application that it is a research focus. The SOI technology is known as the silicon integrated circuit technology of the 21 st century "
Although SOI materials can be successfully used in high-speed, low-power consumer IC products, there are limitations to its use in high-temperature, high-power devices (automobiles, home appliances, and power facilities, etc.). One of the main problems is the spontaneous heating effect, i.e. from the insulating layer SiO2Poor thermal conductivity (thermal conductivity of only about 1% of silicon) causes overheating failure of the device, which can be achieved by using a better thermal conductivity insulating film (Si)3N4,AlN,Al2O3Diamond or DLC, etc.) instead of SiO2The film is solved, wherein the silicon nitride film is higher (than SiO) by virtue of the thermal conductivity thereof2One order of magnitude higher), good insulation, high dielectric constant, high heat dissipation coefficient, compact structure, stable chemical property, simple preparation process, high process compatibility, low cost and the like, and is expected to become a substitute for SiO2Is the only material for insulating buried layer and industrialization.
CVD is commonly used to deposit silicon nitride films at high temperatures, but this method is due to the high post-deposition tensile stress (up to 10)10dyne/cm2) Cracking easily occurs over a certain thickness, and is not suitable for the preparation of SOI materials.
Disclosure of Invention
The invention aims to provide an SOI material taking a nitride film as an insulating buried layer and a preparation method thereof, wherein a silicon nitride film is deposited at a low temperature by a PECVD method to obtain the SOI material taking the nitride film with good heat-conducting property as the insulating buried layer.
In order to achieve the purpose, the invention adopts the technical scheme that:
the SOI material takes a nitride film as an insulating buried layer, and is formed by sequentially compounding a silicon oxynitride film, a silicon nitride film and a silicon oxynitride film. The thickness of the silicon oxynitride film is 10 nm-2 mu m, and the total thickness of the silicon nitride film is 10 nm-10 mu m. The thickness of the top silicon film of the SOI material is 0.02-1.5 μm or 3-250 μm.
The preparation method of the SOI material with the nitride film as the insulating buried layer comprises the following steps:
(1) preparing silicon wafers serving as a device substrate and a support substrate, carrying out plasma in-situ cleaning on the device substrate silicon wafer and the support substrate silicon wafer, and then respectively depositing silicon oxynitride films; the device substrate and the supporting substrate are silicon wafers with any size, crystal phase, conductivity type and resistance;
(2) performing hydrogen plasma etching treatment on the device substrate and the support substrate on which the silicon oxynitride film is deposited, and depositing a silicon nitride film on the surface of the silicon oxynitride film on the device substrate and/or the support substrate;
(3) repeating the process of the step (2) for n times, wherein n is more than or equal to 0(n is an integer) until the total thickness of the deposited silicon nitride film meets the requirement;
(4) after the device substrate and the supporting substrate processed in the step (3) are processed in a mode I or a mode II, the SOI material with the nitride film as the insulating buried layer is obtained; wherein: the process of the mode I comprises the following steps: bonding the device substrate and the supporting substrate, and polishing the obtained bonded piece to obtain an SOI material with the top silicon thickness of 3-250 μm; the process of the mode II comprises the following steps: injecting hydrogen plasma into the device substrate, bonding the device substrate and the supporting substrate, performing microwave sheet splitting on the obtained bonded sheet to form an SOI, and performing CMP (chemical mechanical polishing) treatment on the formed SOI to obtain the SOI material with the top layer silicon thickness of 0.02-1.5 mu m.
In the step (1), the gas used for plasma in-situ cleaning is hydrogen, the hydrogen flow is 50 sccm-100 sccm, and the cleaning time is 10 mm-20 min.
In the step (1), a silicon oxynitride film is deposited by adopting a PECVD method, wherein the required gases are silane, laughing gas, hydrogen and argon, the flow rates are respectively 5 sccm-25 sccm, 2 sccm-20 sccm, 10 sccm-50 sccm and 30 sccm-60 sccm, the deposition pressure is 5-10Pa, the deposition time is 10min-3h, and the deposition thickness is 10 nm-2 microns.
In the step (2), in the hydrogen plasma etching process, the required gas is hydrogen, the flow rate is 60 sccm-100 sccm, and the etching time is 1-12 min.
In the step (2), a silicon nitride film is deposited by adopting a PECVD method, wherein the required gas is silane, ammonia gas, hydrogen gas and argon gas, the flow rates are respectively 5 sccm-25 sccm, 5 sccm-20 sccm, 10 sccm-50 sccm and 30 sccm-60 sccm, the deposition pressure is 5-10Pa, the deposition time is 2min-30min, and the thickness of the deposited silicon nitride film is 10 nm-10 mu m.
The ratio of the thickness of each deposited silicon oxynitride film to the total thickness of the silicon nitride film is less than or equal to 1.
The ratio of the thicknesses of the silicon nitride films deposited on the device substrate and the support substrate is an arbitrary value.
The design principle of the invention is as follows:
the silicon nitride film deposited by the PECVD method contains a plurality of defects such as dislocation, surface state, dangling bond and the like, and the quality of the silicon nitride film is greatly reduced. In the initial growth stage of the silicon nitride film, an amorphous hatching layer is grown, and the nucleation density and the nuclear growth of the silicon nitride film are directly influenced by the defect density of dislocations, surface states, dangling bonds and the like contained in the hatching layer, so that the defect density of the amorphous hatching layer is reduced, the surface activity is increased, and the surface energy is reduced, which is an important link for improving the quality of the silicon nitride film. Therefore, in the deposition process, a hydrogen plasma etching link is added, the etching effect of the hydrogen plasma is utilized, the weak Si-N bond is broken while the silicon dangling bond is filled, the stable Si-N bond is formed again, the surface activity of the film can be increased, the nucleation energy is reduced, and the high-quality silicon nitride film is prepared. In addition, the silicon nitride film is easy to form polycrystal after high-temperature annealing, so that the silicon oxynitride film with certain thickness is deposited before the silicon nitride film is deposited to improve the interface energy of the buried layer, and meanwhile, the SOI warping change caused by the difference of thermal expansion coefficients after the high-temperature annealing can be reduced by regulating the thicknesses of the silicon oxynitride film and the silicon nitride film.
According to the invention, by adopting the method of alternately performing silicon nitride deposition and hydrogen plasma etching and simultaneously adding the silicon oxynitride transition layer, the silicon oxynitride film/silicon nitride film/silicon oxynitride composite film is prepared as the insulating buried layer, and the SOI material with good heat conduction performance is prepared by combining the technical processes of cleaning, injecting, bonding, microwave sheet splitting, annealing, grinding and polishing and the like, so that the problem that the SiO material is used is solved2The SOI device with the thin film as the insulating buried layer has serious self-heating, and simultaneously, the problem of serious SOI warping change caused by high-temperature annealing is reduced.
The invention has the following advantages and beneficial effects:
according to the invention, the silicon nitride film is deposited at low temperature by using a PECVD method, and the quality of the silicon nitride film is increased by combining hydrogen plasma etching and a method for increasing a silicon oxynitride transition layer, so that the internal stress caused by lattice mismatch is reduced, and the warping change of the whole SOI caused by large difference of thermal expansion coefficients during high-temperature annealing is reduced.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
FIG. 2 is a process flow diagram of example 2 of the present invention.
Detailed Description
Example 1:
this example is to prepare an SOI material forming a top silicon film/a silicon oxynitride film/a silicon nitride film/a silicon oxynitride film/a silicon substrate, each layer having a thickness of 20nm/10nm/60nm/10nm/725 μm, respectively. The method comprises the following specific steps:
1) a silicon wafer with 8 inches of P-type resistivity of 8.5-11.5ohm.cm, crystal orientation of <100> and thickness of 725 mu m is selected as a device substrate and a supporting substrate.
2) Sequentially using HF and H2SO4And H2O2The mixed solution and the deionized water sequentially carry out ultrasonic cleaning on the device substrate and the supporting substrate, and the device substrate and the supporting substrate are placed into a reaction chamber of PECVD equipment after being dried.
3) And (3) carrying out hydrogen plasma in-situ cleaning on the device substrate and the supporting substrate, wherein the hydrogen flow is 50sccm, and the cleaning time is 20 min.
4) And depositing a silicon oxynitride film on the device substrate or the support substrate, wherein the used gases are silane, laughing gas, hydrogen and argon, and the flow rates are respectively 5sccm, 2sccm, 50sccm and 60 sccm. The deposition thickness was 10 nm.
5) And carrying out hydrogen plasma etching on the device substrate or the supporting substrate, wherein the hydrogen flow is 60sccm, and the etching time is 2 min.
6) And depositing a silicon nitride film on the surface of the silicon oxynitride film, wherein the used gases are silane, ammonia gas, hydrogen and argon, the flow rates are respectively 5sccm, 50sccm and 60sccm, and the deposition time is 5 min.
7) And (3) performing hydrogen plasma etching on the substrate after the silicon nitride film is deposited, wherein the hydrogen flow is 60sccm, and the etching time is 2 min. .
8) And depositing the silicon nitride film on the surface of the silicon nitride film again, wherein the used gases are silane, ammonia gas, hydrogen and argon, the flow rates are respectively 5sccm, 50sccm and 60sccm, and the deposition thickness is 30 nm.
9) And carrying out hydrogen ion implantation on the device substrate, wherein the implantation depth is 60 nm.
10) And carrying out low-temperature vacuum bonding on the device substrate and the supporting substrate to form a bonding piece.
11) And carrying out low-temperature annealing treatment on the bonding sheet, wherein the annealing temperature is 300 ℃.
12) And performing microwave splitting on the bonded wafer to form the SOI structural material.
13) And finally, carrying out CMP treatment on the top layer silicon to form the SOI material with the top layer thickness of 20 nm.
Example 2:
this example is to prepare SOI material forming top silicon film/silicon oxynitride film/silicon nitride film/silicon oxynitride film/silicon substrate, each layer having a thickness of 13.5 μm/0.5 μm/4 μm/0.5nm/675 μm, respectively. The method comprises the following specific steps:
1) a6-inch silicon wafer with N-type resistivity of 4-7ohm.cm, crystal orientation of <110> and thickness of 675 mu m is selected as a device substrate and a supporting substrate.
2) Sequentially using HF and H2SO4And H2O2The mixed solution and the deionized water sequentially carry out ultrasonic cleaning on the device substrate and the supporting substrate, and the device substrate and the supporting substrate are placed into a reaction chamber of PECVD equipment after being dried.
3) And (3) carrying out hydrogen plasma in-situ cleaning on the device substrate and the supporting substrate, wherein the hydrogen flow is 70sccm, and the cleaning time is 15 min.
4) And depositing a silicon oxynitride film on the device substrate or the support substrate, wherein the used gases are silane, laughing gas, hydrogen and argon, and the flow rates are respectively 15sccm, 8sccm, 30sccm and 30 sccm. The deposition thickness was 0.5 μm.
5) And carrying out hydrogen plasma etching on the device substrate or the supporting substrate, wherein the hydrogen flow is 80sccm, and the etching time is 10 min.
6) And depositing a silicon nitride film on the surface of the silicon oxynitride film, wherein the used gases are silane, ammonia gas, hydrogen and argon, the flow rates are respectively 15sccm, 30sccm and 30sccm, and the deposition time is 10 min.
7) And after the silicon nitride film is deposited, hydrogen plasma etching is carried out, wherein the hydrogen flow is 70sccm, and the etching time is 5 min.
8) And depositing the silicon nitride film on the surface of the silicon nitride film again, wherein the used gases are silane, ammonia gas, hydrogen and argon, the flow rates are respectively 15sccm, 30sccm and 30sccm, and the deposition thickness is 0.5 mu m.
9) And (3) carrying out hydrogen plasma etching on the silicon wafer with the deposited silicon nitride film, wherein the hydrogen flow is 70sccm, and the etching time is 12 min.
10) And depositing the silicon nitride film on the surface of the silicon nitride film again, wherein the used gases are silane, ammonia gas, hydrogen and argon, the flow rates are respectively 15sccm, 30sccm and 30sccm, and the total thickness of the deposited silicon nitride film is 1.5 mu m.
11) And carrying out low-temperature vacuum bonding on the device substrate and the supporting substrate to form a bonding piece.
12) And carrying out high-temperature annealing treatment on the bonding piece, wherein the annealing temperature is 1100 ℃.
13) And finally, carrying out grinding and polishing treatment on the top layer of the bonding sheet to form the SOI material with the top layer silicon thickness of 13.5 mu m.
The SOI materials prepared in the above examples 1 and 2 have a composite structure of silicon oxynitride film/silicon nitride film/silicon oxynitride film as the buried insulating layer, and have a compact structure and a thermal conductivity superior to that of conventional SiO2The SOI with the insulating buried layer is more suitable for the requirements of high-temperature and high-power SOI circuits. In addition, the dielectric constant of silicon nitride is larger than that of SiO2The dielectric constant of (2) can be used as a candidate material of a gate dielectric.
Claims (10)
1. An SOI material with a nitride film as an insulating buried layer is characterized in that: the SOI material takes a nitride film as an insulating buried layer, and the insulating buried layer is formed by sequentially compounding a silicon oxynitride film, a silicon nitride film and a silicon oxynitride film.
2. The SOI material with a buried nitride film as a buried insulating layer according to claim 1, wherein: the thickness of the silicon oxynitride film is 10 nm-2 mu m, and the total thickness of the silicon nitride film is 10 nm-10 mu m.
3. The SOI material with a buried nitride film as a buried insulating layer according to claim 1 or 2, wherein: the thickness of the top silicon film of the SOI material is 0.02-1.5 μm or 3-250 μm.
4. The method according to claim 1, wherein said SOI material comprises a buried nitride film as an insulating layer, and further comprises: the method comprises the following steps:
(1) preparing silicon wafers serving as a device substrate and a support substrate, carrying out plasma in-situ cleaning on the device substrate silicon wafer and the support substrate silicon wafer, and then respectively depositing silicon oxynitride films;
(2) performing hydrogen plasma etching treatment on the device substrate and the support substrate on which the silicon oxynitride film is deposited, and depositing a silicon nitride film on the surface of the silicon oxynitride film on the device substrate and/or the support substrate;
(3) repeating the process of the step (2) for n times, wherein n is not less than 0 and is an integer until the total thickness of the deposited silicon nitride film meets the requirement;
(4) after the device substrate and the supporting substrate processed in the step (3) are processed in a mode I or a mode II, the SOI material with the nitride film as the insulating buried layer is obtained; wherein: the process of the mode I comprises the following steps: bonding the device substrate and the supporting substrate, and polishing the obtained bonded piece to obtain an SOI material with the top silicon thickness of 3-250 μm; the process of the mode II comprises the following steps: injecting hydrogen plasma into the device substrate, bonding the device substrate and the supporting substrate, performing microwave sheet splitting on the obtained bonded sheet to form an SOI, and performing CMP (chemical mechanical polishing) treatment on the formed SOI to obtain the SOI material with the top layer silicon thickness of 0.02-1.5 mu m.
5. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: in the step (1), the gas used for plasma in-situ cleaning is hydrogen, the hydrogen flow is 50 sccm-100 sccm, and the cleaning time is 10 mm-20 min.
6. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: in the step (1), a silicon oxynitride film is deposited by adopting a PECVD method, wherein the required gases are silane, laughing gas, hydrogen and argon, the flow rates are respectively 5 sccm-25 sccm, 2 sccm-20 sccm, 10 sccm-50 sccm and 30 sccm-60 sccm, the deposition pressure is 5-10Pa, the deposition time is 10min-3h, and the deposition thickness is 10 nm-2 microns.
7. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: in the step (2), in the hydrogen plasma etching process, the required gas is hydrogen, the flow rate is 60 sccm-100 sccm, and the etching time is 1-12 min.
8. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: in the step (2), a silicon nitride film is deposited by adopting a PECVD method, wherein the required gas is silane, ammonia gas, hydrogen gas and argon gas, the flow rates are respectively 5 sccm-25 sccm, 5 sccm-20 sccm, 10 sccm-50 sccm and 30 sccm-60 sccm, the deposition pressure is 5-10Pa, the deposition time is 2min-30min, and the thickness of the deposited silicon nitride film is 10 nm-10 mu m.
9. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: the ratio of the thickness of each deposited silicon oxynitride film to the total thickness of the silicon nitride film is less than or equal to 1.
10. The method for preparing an SOI material with a buried nitride film as an insulating layer according to claim 4, wherein: the ratio of the thicknesses of the silicon nitride films deposited on the device substrate and the support substrate is an arbitrary value.
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