CN103839800A - Method for producing silicon nitride - Google Patents
Method for producing silicon nitride Download PDFInfo
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- CN103839800A CN103839800A CN201210473382.0A CN201210473382A CN103839800A CN 103839800 A CN103839800 A CN 103839800A CN 201210473382 A CN201210473382 A CN 201210473382A CN 103839800 A CN103839800 A CN 103839800A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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Abstract
本发明公开了一种氮化硅制造方法，包括：步骤c1，通入氨气和氮气并预稳定；步骤c2，通入硅烷；步骤c3，射频点火；步骤c4，沉积氮化硅；步骤c5，氮气等离子体处理氮化硅。依照本发明的张应力氮化硅制造方法，采用氮气等离子轰击来增强Si-N键合力从而提高薄膜密度，提高了张应力氮化硅的抗酸性，使其能适用于集成在双应变衬层后栅工艺中，有效提高了器件的性能和可靠性。
The invention discloses a silicon nitride manufacturing method, comprising: step c1, feeding ammonia and nitrogen and pre-stabilizing; step c2, feeding silane; step c3, radio frequency ignition; step c4, depositing silicon nitride; step c5 , nitrogen plasma treatment of silicon nitride. According to the tensile stress silicon nitride manufacturing method of the present invention, the nitrogen plasma bombardment is used to enhance the Si-N bonding force to increase the film density, improve the acid resistance of the tensile stress silicon nitride, and make it suitable for integration in double-strain liners In the gate-last process, the performance and reliability of the device are effectively improved.
Description
Technical field
The present invention relates to a kind of method, semi-conductor device manufacturing method, particularly relate to a kind of strain silicon nitride manufacture method with tensile stress.
Background technology
In the time of the long lasting reduction of device physics grid, make device still can keep good performance if attempt, carrier mobility enhancing technology is vital for CMOS scaled down.
Strained silicon technology has improved the switching speed of device by only strengthening carrier mobility, become the focus of current research.
In high performance logic technology, extensively adopt coaxial technique strained silicon in the recent period.Research and develop by the tensile stress nitride cap on device architecture and introduced channel strain, thereby strengthened NMOS carrier mobility.Similarly, can on device architecture, form compression nitride cap to strengthen PMOS carrier mobility.Adopt above-mentioned existing technology, for NMOS, in silicon nitride film, produced by above-mentioned technique and induced the tensile stress up to about 1.4GPa obtaining, for PMOS, produced the compression up to about 3.0GPa.
Above-mentioned pair of strain lining integrated technique not only needs high silicon nitride strain, and after using, also need when grid technique film to there is good density and acid-resisting (for example, for dilute hydrofluoric acid dHF, particularly in the time that rear grid technique is removed false grid and pad oxide thereof, the acid of corrosion use may make stressor layers have larger and even unacceptable damage, has had a strong impact on the performance of device).Following table 1 is the comparison between corrosion of various common materials under dHF.
Table 1
As can be seen here, under same etching condition, tensile stress silicon nitride etch rate in dHF obviously exceedes compression silicon nitride and thermal oxide, makes to be difficult to integrated employing tensile stress silicon nitride in two strain linings of rear grid technique.
Summary of the invention
Therefore, the object of the invention is to overcome above-mentioned difficulties, a kind of manufacture method that can effectively strengthen tensile stress silicon nitride film density and stress is provided.
The invention provides a kind of silicon nitride manufacture method, comprising: step c1, passes into ammonia and nitrogen precondition; Step c2, passes into silane; Step c3, radio frequency igniting; Step c4, deposited silicon nitride; Step c5, nitrogen plasma treatment silicon nitride.
Wherein, cyclically repeated execution of steps c1 to step c5.
Wherein, cycle-index is 20 times.
Wherein, after each step c4, all perform step c5.
Wherein, step c1 is to the stable 6T that is controlled at of cavity pressure in step c5 implementation.
Wherein, in step c1, ammonia flow is 80sccm, and nitrogen flow is 4000sccm, and duration of ventilation is 10s.
Wherein, in step c2, in the flow while that keeps step c1, passing into silane flow rate is 20sccm, duration of ventilation 5s.
Wherein, in step c3, in the flow while that keeps step c1 and step c2, excite radio frequency, open high-frequency RF, be set as 40W, the time is 5s.
Wherein, in step c4, keeping under the condition of step c3, sedimentation time is 1.5s, and deposition thickness is
Wherein, in step c5, close ammonia and silane, continue to pass into nitrogen, open high-frequency RF 40W, excite nitrogen plasma bombardment silicon nitride film.
Wherein, before step c1, further comprise: step a, cleans and adjusts cavity; Step b, loaded with wafers.
Wherein, step a 120s consuming time, step b 5s consuming time.
Wherein, after step c5, further comprise: turn off low frequency RF and reacting gas, pass into nitrogen until normal pressure takes out wafer.
Wherein, in cavity, temperature is 200～550 ℃.
Wherein, RF low frequency is 106～188KHZ, and high frequency is 13.56MHz.
Wherein, in cavity, base vacuum degree is less than or equal to 30mT.
Wherein, adopt double frequency capacitively coupled plasma parallel plate type PECVD equipment.
According to tensile stress silicon nitride manufacture method of the present invention, thereby adopt nitrogen plasma to bombard to strengthen Si-N bonding force and improve density of film, improve the acid-resisting of tensile stress silicon nitride, can be applicable to be integrated in after two strain linings in grid technique, effectively improve the Performance And Reliability of device.
Accompanying drawing explanation
Describe technical scheme of the present invention in detail referring to accompanying drawing, wherein:
Fig. 1 is the schematic flow diagram according to method of the present invention.
Embodiment
The feature and the technique effect thereof that describe technical solution of the present invention in detail referring to accompanying drawing and in conjunction with schematic embodiment, disclose the manufacture method that can effectively strengthen tensile stress silicon nitride film density and stress.It is pointed out that structure like similar Reference numeral representation class, term " first " used in the application, " second ", " on ", D score etc. can be used for modifying various device architectures or processing step.These modify the space, order or the hierarchical relationship that not imply unless stated otherwise institute's modification device architecture or processing step.
In one embodiment of the invention, the method for deposition tensile stress silicon nitride film is to adopt pecvd process, and the equipment of employing is double frequency capacitively coupled plasma parallel plate type PECVD equipment.In addition, other embodiment of the present invention also can adopt other equipment and deposition process, the equipment such as such as PECVD (different board-like or different coupled modes), HDPCVD, MBE, ALD, as long as comprised the step of nitrogen plasma bombardment of the present invention in method.
In one embodiment of the invention, in PECVD equipment cavity, temperature is controlled at approximately 200～550 ℃ and preferably 400 ℃, and the control of radio frequency (RF) low frequency is approximately 106～188KHz preferably 158KHz, and high frequency control is about 13.56MHz.Equipment cavity adopts the equipment such as molecular pump, ionic pump to vacuumize, and the ideal value of background, close to 0 (background air pressure is about 0 in chamber), according to the ability of vaccum-pumping equipment, is preferably so that base vacuum degree is less than or equal to 30mT in reality.
Figure 1 shows that the process method flow chart according to one embodiment of the invention, it should be noted that, each step shown in figure is except " deposition " and " nitrogen treatment " step is necessary, all the other each steps are all preferred, and sequencing and number of repetition between these steps can be also optional.
Step a, cleans and adjusts (season) cavity.Pass into the inert gas such as nitrogen or Ar gas, and (for example carbon fluorine base gas is (as CF can to add fluorine-containing compound
4, CH
2f
2, CH
3f, CHF
3), XeF etc.) to strengthen cleaning capacity, purge cavity, remove residual last time product in cavity and on cavity wall.After passing into clean air, can suitably improve temperature to promote cleaning capacity, and preferably keep certain hour to adjust cavity, make inside cavity reach balanced (temperature, pressure and other parameters are evenly distributed) everywhere.The duration of step a is for example about 120s.
Step b, loaded with wafers.Open the door of apparatus cavity, manipulator robot or other clamping devices, be sent to single wafer or multiple wafer (parallel being placed in wafer case or similar fixture) in cavity and fix.The duration of step b is about 5s.
Step c1, passes into the first reacting gas and stable in advance.Open the first valve, pass into the first reacting gas as nitrogen element source, and open the 3rd valve and pass into nitrogen (N
2).In one embodiment of the invention, the first reacting gas is NH
3.Pass into N
2and NH
3the time of gas is about 10s.N
2with NH
3gas flow is respectively the N of about 80sccm
2and the NH of about 4000sccm
3.Pass into the second gas that gas does not pass into element silicon source immediately, but keep a period of time, make the first reacting gas and nitrogen in cavity, spread homogenizing, make the pressure stability in cavity be maintained at about 6T.
Step c2, passes into the second reacting gas.In keeping the flow that passes into the first gas of step c1, open the second valve, pass into the second reacting gas as element silicon source, be for example silane (SiH
4).The flow of the second gas is about 20sccm, and the time is for example 5s, and makes the stable 6T that remains on of cavity internal pressure.
Step c3, radio frequency (RF) igniting.Keep step c1 and c2 reacting gas flow and make that cavity internal pressure is stable and remain on 6T in, excite radio frequency, open high-frequency RF, be set as 40W, the time is 5s.
Step c4, deposited silicon nitride.Under the condition that keeps step c1～c3, carry out the deposition of film, i.e. first circulation (cycle).The time of step c4 is set as 1.5s, and the film thickness of the silicon nitride depositing on wafer is about
the now stable 6T that is maintained at about of cavity pressure.
Step c5, nitrogen treatment.Close NH
3and SiH
4the first and second valves of unstripped gas, keep the 3rd valve opening of nitrogen, continue to pass into the nitrogen of 4000sccm, open high-frequency RF 40W, the silicon nitride film surface that excites N plasma bombardment step c4 to form, improves density of film thereby strengthen Si-N bonding force, has improved the acid-resisting of tensile stress silicon nitride, can be applicable to be integrated in after two strain linings in grid technique, effectively improve the Performance And Reliability of device.Now, cavity pressure is stable is controlled at about 6T.
Preferably, cyclically repeated execution of steps c1 is to step c5, to make silicon nitride film reach desired thickness.In one embodiment of the invention, it is 20 times that step c1 carries out number of times to the circulation of step c5.It should be noted that, the nitrogen treatment of step h can be arbitrary number of times, and to the cyclic program of step c5, be positioned at any order at step c1, for example can after each step c4, all perform step c5 to obtain optimum efficiency, but also can only after optional several step c4, just perform step c5, for example, initial and finally just perform step c5 after step c4 in several (5) circulation, so make at least top layer of silicon nitride film entirety improve acid-resisting such as only.But, preferably, in order to make the acid-resisting optimization of tensile stress silicon nitride, after each step c4, all perform step c5, make each silicon nitride sublayer all improve acid-resisting.
Steps d, finishes.After having experienced required repeatedly circulation, close low frequency RF and reacting gas, pass into nitrogen until cavity pressure reverts to normal pressure (atmospheric pressure), open hatch door, utilize pick device to take out wafer, complete whole silicon nitride deposition process.
Following table 2 has been listed through the acid-resisting comparison between nitrogen treatment and undressed tensile stress silicon nitride:
Table 2
As can be seen here, nitrogen plasma treatment has reduced the corrosion rate of silicon nitride in dHF, and its acid-resisting is significantly improved, and is conducive to be integrated into the technique of dual stress liner, has improved the reliability of device.In addition, due to nitrogen gas plasma bombardment silicon nitride surface, the stress of silicon nitride sublayer is improved, the stress of the final silicon nitride film forming is promoted to through the 1200MPa after processing from undressed 900MPa, improve tensile stress, promote carrier mobility further to promote, improved the performance of device.
According to tensile stress silicon nitride manufacture method of the present invention, thereby adopt nitrogen plasma to bombard to strengthen Si-N bonding force and improve density of film, improve the acid-resisting of tensile stress silicon nitride, can be applicable to be integrated in after two strain linings in grid technique, effectively improve the Performance And Reliability of device.
Although with reference to one or more exemplary embodiments explanation the present invention, those skilled in the art can know without departing from the scope of the invention device architecture and/or technological process are made to various suitable changes and equivalents.In addition, can make and manyly may be suitable for the modification of particular condition or material and not depart from the scope of the invention by disclosed instruction.Therefore, object of the present invention does not lie in and is limited to as the disclosed specific embodiment for realizing preferred forms of the present invention, and disclosed device architecture and manufacture method thereof will comprise all embodiment that fall in the scope of the invention.
Claims (17)
1. a silicon nitride manufacture method, comprising:
Step c1, passes into ammonia and nitrogen precondition;
Step c2, passes into silane;
Step c3, radio frequency igniting;
Step c4, deposited silicon nitride;
Step c5, nitrogen plasma treatment silicon nitride.
2. silicon nitride manufacture method as claimed in claim 1, wherein, cyclically repeated execution of steps c1 is to step c5.
3. silicon nitride manufacture method as claimed in claim 2, wherein, cycle-index is 20 times.
4. silicon nitride manufacture method as claimed in claim 2 wherein, all performs step c5 after each step c4.
5. silicon nitride manufacture method as claimed in claim 1, wherein, step c1 is to the stable 6T that is controlled at of cavity pressure in step c5 implementation.
6. silicon nitride manufacture method as claimed in claim 1, wherein, in step c1, ammonia flow is 80sccm, and nitrogen flow is 4000sccm, and duration of ventilation is 10s.
7. silicon nitride manufacture method as claimed in claim 6, wherein, in step c2, in the flow while that keeps step c1, passing into silane flow rate is 20sccm, duration of ventilation 5s.
8. silicon nitride manufacture method as claimed in claim 7, wherein, in step c3, in the flow while that keeps step c1 and step c2, excites radio frequency, opens high-frequency RF, is set as 40W, and the time is 5s.
9. silicon nitride manufacture method as claimed in claim 8, wherein, in step c4, is keeping under the condition of step c3, and sedimentation time is 1.5s, and deposition thickness is
10. silicon nitride manufacture method as claimed in claim 1, wherein, in step c5, closes ammonia and silane, continues to pass into nitrogen, opens high-frequency RF 40W, excites nitrogen plasma bombardment silicon nitride film.
11. silicon nitride manufacture methods as claimed in claim 1, wherein, further comprise before step c1:
Step a, cleans and adjusts cavity;
Step b, loaded with wafers.
12. as the silicon nitride manufacture method of claim 11, wherein, and step a 120s consuming time, step b 5s consuming time.
13. silicon nitride manufacture methods as claimed in claim 1, wherein, further comprise after step c5: turn off low frequency RF and reacting gas, pass into nitrogen until normal pressure takes out wafer.
14. silicon nitride manufacture methods as claimed in claim 1, wherein, in cavity, temperature is 200～550 ℃.
15. silicon nitride manufacture methods as claimed in claim 1, wherein, RF low frequency is 106～188KHZ, high frequency is 13.56MHz.
16. silicon nitride manufacture methods as claimed in claim 1, wherein, in cavity, base vacuum degree is less than or equal to 30mT.
17. silicon nitride manufacture methods as claimed in claim 1, wherein, adopt double frequency capacitively coupled plasma parallel plate type PECVD equipment.
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Cited By (9)
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| CN105702575A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院微电子研究所 | Semiconductor device manufacturing method |
| CN105712305A (en) * | 2014-12-02 | 2016-06-29 | 沈阳鑫劲粉体工程有限责任公司 | New silicon nitride powder synthesis method |
| CN106058071A (en) * | 2016-07-01 | 2016-10-26 | 沈阳拓荆科技有限公司 | Barrier layer structure of OLED device and preparation method thereof |
| CN106356337A (en) * | 2015-07-17 | 2017-01-25 | 中芯国际集成电路制造(上海)有限公司 | Manufacturing method of semiconductor apparatus |
| CN110473768A (en) * | 2018-05-09 | 2019-11-19 | 上海新微技术研发中心有限公司 | The preparation method of silicon nitride film |
| US20200006277A1 (en) * | 2018-06-29 | 2020-01-02 | Yangtze Memory Technologies Co., Ltd. | Semiconductor structure and forming method thereof |
| US20200006278A1 (en) * | 2018-06-29 | 2020-01-02 | Yangtze Memory Technologies Co., Ltd. | Semiconductor structure and method of forming the same |
| CN112420731A (en) * | 2020-11-17 | 2021-02-26 | 长江存储科技有限责任公司 | Method for forming thin film layer in deep hole and method for manufacturing semiconductor device |
| CN116254518A (en) * | 2023-05-10 | 2023-06-13 | 上海陛通半导体能源科技股份有限公司 | Preparation method of silicon nitride film |
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| CN105702575A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院微电子研究所 | Semiconductor device manufacturing method |
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| US20200006278A1 (en) * | 2018-06-29 | 2020-01-02 | Yangtze Memory Technologies Co., Ltd. | Semiconductor structure and method of forming the same |
| US20200006277A1 (en) * | 2018-06-29 | 2020-01-02 | Yangtze Memory Technologies Co., Ltd. | Semiconductor structure and forming method thereof |
| US10818631B2 (en) * | 2018-06-29 | 2020-10-27 | Yangtze Memory Technologies Co., Ltd. | Semiconductor structure and method of forming the same |
| CN112567512A (en) * | 2018-06-29 | 2021-03-26 | 长江存储科技有限责任公司 | Semiconductor structure and forming method thereof |
| CN112567512B (en) * | 2018-06-29 | 2023-09-01 | 长江存储科技有限责任公司 | Semiconductor structure and forming method thereof |
| CN112420731A (en) * | 2020-11-17 | 2021-02-26 | 长江存储科技有限责任公司 | Method for forming thin film layer in deep hole and method for manufacturing semiconductor device |
| CN112420731B (en) * | 2020-11-17 | 2021-12-17 | 长江存储科技有限责任公司 | Method for forming thin film layer in deep hole and method for manufacturing semiconductor device |
| CN116254518A (en) * | 2023-05-10 | 2023-06-13 | 上海陛通半导体能源科技股份有限公司 | Preparation method of silicon nitride film |
| CN116254518B (en) * | 2023-05-10 | 2023-08-18 | 上海陛通半导体能源科技股份有限公司 | Preparation method of silicon nitride film |
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