CN116313525A - Preparation method of metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability - Google Patents
Preparation method of metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability Download PDFInfo
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- CN116313525A CN116313525A CN202310439467.5A CN202310439467A CN116313525A CN 116313525 A CN116313525 A CN 116313525A CN 202310439467 A CN202310439467 A CN 202310439467A CN 116313525 A CN116313525 A CN 116313525A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- 239000003990 capacitor Substances 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 238000004544 sputter deposition Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 15
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 12
- 230000005669 field effect Effects 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910004140 HfO Inorganic materials 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003749 cleanliness Effects 0.000 claims description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/06—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture having a dielectric selected for the variation of its permittivity with applied voltage, i.e. ferroelectric capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to the technical field of varactors, in particular to a preparation method of a metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability. It includes S1: after cleaning and drying the semiconductor substrate to be sputtered, placing the substrate on a sputtering table; s2: the angle of the target in the vacuum chamber is adjusted to a preset angle, and the distance between the target and the substrate is synchronously adjusted to a preset distance; s3: vacuumizing the vacuum chamber to reach the appointed background vacuum; s4: heating the substrate to a specified working temperature, and maintaining the temperature until the substrate is heated uniformly; s5: adjusting the gas proportion and the gas pressure of the working environment, and sputtering a ferroelectric film on the substrate; s6: after the film sputtering is finished, heating the substrate to an annealing temperature, and annealing in an oxygen environment; s7: and after the device is naturally cooled, preparing an upper electrode on one side of the ferroelectric film. The invention has simple process, simple equipment, low cost and mass production, and has great application prospect in the fields of adjustable acoustic devices, MFS transistors and the like.
Description
Technical Field
The invention relates to the technical field of varactors, in particular to a preparation method of a metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability.
Background
Varactors, also known as tunable capacitors, have potential applications throughout the field of communication technology. In the fields of radio frequency front ends, 5G, the Internet of things (LoT) and the like, the varistors play a key role in bulk acoustic wave resonators and tunable surface acoustic wave filters. The higher tunability of the tunable capacitor means a wider range of band selection, higher efficiency and cost. However, the current varactors have the problems of low adjustable rate, large volume and the like, and severely limit the application of the varactors in the technical field of communication.
For the above reasons, the metal-ferroelectric-semiconductor varactors prepared on a semiconductor substrate according to the present invention combine the electro-effect of ferroelectric materials with the field effect of semiconductors. Under the bias voltage of-5V to 5V, the adjustable rate reaches 25, the adjustable rate which can be achieved by far exceeding the maximum adjustable capacitance is achieved, the thickness of the film is only 200 nanometers, and the film has smaller volume. The invention has simple process, simple equipment, low cost and mass production, and has wide application prospect in the fields of adjustable acoustic devices, field effect transistors and the like.
Disclosure of Invention
The invention aims at solving the problems in the background art, and provides a preparation method of a metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability. The method can be directly compatible with the semiconductor manufacturing process, and has wide prospect in the communication technical fields of adjustable acoustic devices, radio frequency microwave devices and the like.
The technical scheme of the invention is that the preparation method of the metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability comprises the following steps:
s1: after cleaning and drying the semiconductor substrate to be sputtered, placing the substrate on a sputtering table;
s2: the angle of the target in the vacuum chamber is adjusted to a preset angle, and the distance between the target and the substrate is synchronously adjusted to a preset distance;
s3: vacuumizing the vacuum chamber to reach the appointed background vacuum;
s4: heating the substrate to a specified working temperature, and maintaining the temperature until the substrate is heated uniformly;
s5: adjusting the gas proportion and the gas pressure of the working environment, and sputtering a ferroelectric film on the substrate;
s6: after the film sputtering is finished, heating the substrate to an annealing temperature, and annealing in an oxygen environment;
s7: and after the device is naturally cooled, preparing an upper electrode on one side of the ferroelectric film.
Preferably, in S1, cleaning the semiconductor substrate to be sputtered to remove a natural silicon dioxide layer, organic matters and residual chemical cleaning solvent on the substrate; and thoroughly drying the cleaned substrate.
Preferably, the semiconductor substrate in S1 is a material capable of triggering metal-ferroelectric-semiconductor field effect, and further preferably, all first, second and third generation semiconductors or materials with semiconductor properties can be used as substrates; still more preferably, the semiconductor substrate is selected from silicon, gallium nitride or silicon carbide.
Preferably, in S2: the preset angle and the preset distance are adjusted according to the required film growth speed.
Preferably, in S3: the background vacuum is the vacuum degree in the vacuum chamber before sputtering and is 1x10 -4 Pa or less to reduce the interference of impurities in the vacuum chamber on film growth.
Preferably, in S4: the specified sputtering temperature is 350 ℃ and above, and the substrate is heated uniformly and then the process goes to step S5.
Preferably, in S5: the ferroelectric layer material selected for sputtering is selected from barium strontium titanate, lead zirconate titanate, barium titanate and HfO 2 Etc., but are not limited to these materials. Materials with better ferroelectric properties can be used as the material of the ferroelectric layer.
Preferably, in S5: closing a sample baffle, performing pre-sputtering, performing pre-treatment on the surface of the ferroelectric material target, and performing main sputtering on the substrate; the sputtering time and power can be adjusted according to the sputtering rate of different materials. The thickness of the sputtered ferroelectric film should be in the range of 50nm-500nm, and the film crystallization is good.
Preferably, in step S6, before annealing, the gas introduced during sputtering needs to be pumped down, and oxygen is introduced after ensuring the cleanliness in the vacuum chamber, so that the oxygen pressure in the vacuum chamber reaches above 60000 Pa; heating to the designated annealing temperature and ensuring that the substrate is heated uniformly, waiting for the temperature to naturally cool and then starting sputtering the electrode.
Preferably, the work function of the electrode material described in S7 is greater than that of silicon. Further, the electrode material is preferably selected from Pt, au, ag, and other materials having good conductivity.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention adopts a magnetron sputtering method to prepare the barium strontium titanate film, and the magnetron sputtering is used as one of PVD (physical vapor deposition) films, is mainly used for depositing various functional films, is widely applied to the semiconductor fields of integrated circuits, solar cells, LEDs, flat panel displays and the like, solves the problem of poor crystallization of the barium strontium titanate film on a semiconductor substrate, and has the advantages of low cost, better film forming quality, suitability for mass production and the like.
2. The capacitor prepared on the silicon substrate by the method has the adjustable rate of 25 under the bias voltage of-5V to 5V, and has high capacitance adjustability.
3. The barium strontium titanate film grown on the silicon substrate by the method of the invention has 230nm, the thickness of the electrode is 50nm, the device volume is small, and the like, which is beneficial to the integration of the varistors on the chip.
Drawings
Fig. 1 is a process flow diagram of example 1 of the present invention.
FIG. 2 is a diagram showing the structure of a varactor prepared in example 1 of the present invention; .
FIG. 3 is a cross-sectional SEM image of a barium strontium titanate nano-film directly prepared on a silicon substrate in example 1 of the present invention.
Fig. 4 is a graph showing the change of capacitance with voltage of the capacitor prepared in example 1 of the present invention.
Reference numerals illustrate:
FIG. 3 shows a cross-sectional SEM image of a barium strontium titanate nanofilm directly prepared on a silicon substrate, where the barium strontium titanate film thickness was directly observed to be 230nm.
The graph of capacitance versus voltage for the capacitor prepared in fig. 4 shows that the maximum capacitance of the device is 4.8nF and the minimum capacitance is 0.19nF at a bias voltage of-5V to 5V, and the tunable ratio can reach 25.
Detailed Description
Example 1
The invention provides a preparation method of a metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability, wherein a semiconductor substrate material is silicon, a silicon substrate needs to be cleaned by hydrofluoric acid to remove a natural silicon dioxide layer before sputtering, then acetone is used for cleaning organic matters on the surface of the substrate, and finally alcohol is used for cleaning acetone. The ultrasonic cleaning technology is used in the cleaning steps, and after the cleaning steps are finished, the surface of the substrate is dried by utilizing nitrogen.
And (3) adjusting the angle of the target in the vacuum chamber to be 45 degrees in the vertical direction on a preset angle, and mounting the substrate and the target after adjusting the distance between the target and the substrate to be 160 mm. Then the vacuumizing step is started to wait for the local vacuum degree to reach 9x10 -5 After Pa, heating of the silicon substrate is started. After the heating temperature reached 680 degrees, the temperature was maintained for 30 minutes. Starting to introduce gas, and setting the sputtering gas environment of the sample as follows: argon-oxygen ratio is 21:9; the operating air pressure was 0.4Pa. And closing the sample baffle, and pre-sputtering the barium strontium titanate target material. The ratio of barium and strontium elements in the barium strontium titanate target material is 0.7:0.3, and the purity reaches 99.995%; the barium strontium titanate target as a nonmetallic target needs to be pre-sputtered for 10 minutes at a power of 80W. After the pre-sputtering is finished, the sputtering frequency is adjusted to be 100W, a sample baffle is opened, and the main sputtering of the barium strontium titanate is started, wherein the sputtering time is 180 minutes.
And after sputtering is finished, a sputtering power supply is turned off, and annealing treatment is started, so that the film quality is further improved. Firstly, the gas introduced during sputtering is pumped out before annealing, and the background vacuum degree is 9x10 -5 And after Pa, starting to introduce oxygen so that the oxygen pressure in the vacuum chamber reaches 70000Pa. After which startHeating to the specified annealing temperature of 700 ℃ and continuing heating for 30 minutes after the temperature rises to 700 ℃, turning off a heating power supply after the silicon substrate is heated uniformly, and sputtering an electrode after waiting for natural cooling of the temperature.
The electrode material is platinum, and the purity reaches 99.995 percent. And closing a sample baffle, performing pre-sputtering, and performing pre-treatment on the surface of the platinum target to remove an oxide layer and pollutants on the surface of the target. In the main sputtering and the pre-sputtering, the radio frequency sputtering power is 60W, the pre-sputtering time is 10 minutes, the main sputtering time is 3 minutes after the pre-sputtering is completed, the sputtering is performed in the pure argon environment, and the working air pressure is 0.7Pa. After the preparation of the device is finished, the device is subjected to electrical test and SEM characterization, and the result shows that the adjustable rate reaches 25, and the film thickness is 230nm.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited thereto, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability is characterized by comprising the following steps:
s1: after cleaning and drying the semiconductor substrate to be sputtered, placing the substrate on a sputtering table;
s2: the angle of the target in the vacuum chamber is adjusted to a preset angle, and the distance between the target and the substrate is synchronously adjusted to a preset distance;
s3: vacuumizing the vacuum chamber to reach the appointed background vacuum;
s4: heating the substrate to a specified working temperature, and maintaining the temperature until the substrate is heated uniformly;
s5: adjusting the gas proportion and the gas pressure of the working environment, and sputtering a ferroelectric film on the substrate;
s6: after the film sputtering is finished, heating the substrate to an annealing temperature, and annealing in an oxygen environment;
s7: and after the device is naturally cooled, preparing an upper electrode on one side of the ferroelectric film.
2. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S1, the semiconductor substrate to be sputtered is cleaned to remove a natural silicon dioxide layer, organics and residual chemical cleaning solvent on the substrate; and thoroughly drying the cleaned substrate.
3. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein the semiconductor substrate in S1 is made of a material capable of triggering metal-ferroelectric-semiconductor field effect.
4. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S2: the preset angle and the preset distance are adjusted according to the required film growth speed.
5. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S3: the background vacuum is the vacuum degree in the vacuum chamber before sputtering and is 1x10 -4 Pa or below.
6. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S4: the specified sputtering temperature is 350 ℃ and above, and the substrate is heated uniformly and then the process goes to step S5.
7. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S5: the material of the sputtered ferroelectric layer can be selected from barium strontium titanate, lead zirconate titanate, barium titanate and HfO 2 。
8. The method for manufacturing a metal ferroelectric semiconductor field effect tunable capacitor with high capacitance tunability according to claim 1, wherein in S5: closing a sample baffle, performing pre-sputtering, performing pre-treatment on the surface of the ferroelectric material target, and performing main sputtering on the substrate; the sputtering time and the power can be adjusted according to the sputtering rates of different materials; the thickness of the sputtered ferroelectric film should be in the range of 50nm-500 nm.
9. The method for manufacturing the metal ferroelectric semiconductor field effect adjustable capacitor with high capacitance adjustability according to claim 1, wherein the step S6 is characterized in that before annealing, the gas introduced during sputtering is pumped out, the oxygen is introduced after ensuring the cleanliness in the vacuum chamber, and the oxygen pressure in the vacuum chamber is up to 60000 Pa; heating to the designated annealing temperature and ensuring that the substrate is heated uniformly, waiting for the temperature to naturally cool and then starting sputtering the electrode.
10. A method of producing a metal-ferroelectric-semiconductor varactor with high capacitance tunability by magnetron sputtering according to claim 1, characterized in that the work function of the electrode material in S7 is larger than that of silicon.
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| CN202310439467.5A CN116313525A (en) | 2023-04-23 | 2023-04-23 | Preparation method of metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability |
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| CN202310439467.5A CN116313525A (en) | 2023-04-23 | 2023-04-23 | Preparation method of metal ferroelectric semiconductor adjustable capacitor with high capacitance adjustability |
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