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  • 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
  • H01L21/02126—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 containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
  • H01L21/0214—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 containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
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  • 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
  • H01L21/02164—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 oxide, e.g. SiO2
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  • 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
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02551—Group 12/16 materials
  • H01L21/02554—Oxides
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/28008—Making conductor-insulator-semiconductor electrodes
  • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
  • H01L21/28158—Making the insulator
  • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
  • H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
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  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/28008—Making conductor-insulator-semiconductor electrodes
  • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
  • H01L21/28158—Making the insulator
  • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
  • H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
• • H—ELECTRICITY
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  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/28008—Making conductor-insulator-semiconductor electrodes
  • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
  • H01L21/28158—Making the insulator
  • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
  • H01L21/28211—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a gaseous ambient using an oxygen or a water vapour, e.g. RTO, possibly through a layer
• • H—ELECTRICITY
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3105—After-treatment
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  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D64/00—Electrodes of devices having potential barriers
  • H10D64/01—Manufacture or treatment
  • H10D64/031—Manufacture or treatment of data-storage electrodes
  • H10D64/035—Manufacture or treatment of data-storage electrodes comprising conductor-insulator-conductor-insulator-semiconductor structures

Definitions

• the present invention relates to semiconductor substrate processing and, more particularly, to a method for low-temperature dielectric film deposition using a chlorinated silane and water vapor.
• oxide or oxynitride films are frequently grown or deposited over the surface of a crystalline substrate such as silicon.
• Industry standard processes for chemical vapor deposition (CVD) of high quality silicon oxide (SiO x , x ⁇ 2) films for semiconductor Flash memory and micro-feature sidewall applications are based on high-temperature reactions of dichlorosilane (DCS) and nitrous oxide (N 2 0), for example.
• DCS dichlorosilane
• N 2 0 nitrous oxide
• the main benefits of this process include the ability to process multiple substrates simultaneously in a batch process, excellent electrical performance of the silicon oxide films, and relatively low wet etch rates of the films compared to other CVD films, e.g., films deposited using tetraethyl orthosilicate (TEOS), bis(tertiary-butylamino)silane (BTBAS), and other precursors.
• TEOS tetraethyl orthosilicate
• BBAS bis(tertiary-butylamino)silane
• oxide films e.g., oxide films on silicon and germanium
• nitrogen incorporation into the oxide films increases the dielectric constant of the resulting oxynitride film, and allows thinner gate dielectrics to be grown on these semiconductor substrate materials.
• Silicon oxynitride (SiO x N y ) films can have good electrical properties, including high electron mobility and low electron trap density that are desirable for device operation in semiconductor applications.
• One embodiment of the invention provides a method for low-temperature CVD of silicon oxide films on a plurality of substrates in a batch processing system using dichlorosilane (DCS) and water vapor.
• the method includes positioning a plurality of substrates in a process chamber, heating the process chamber to a deposition temperature between 400°C and less than 650°C, flowing a first process gas comprising water vapor into the process chamber, flowing a second process gas comprising dichlorosilane (DCS) into the process chamber, establishing a gas pressure of less than 2 Torr in the process chamber, and reacting the first and second process gases to thermally deposit a silicon oxide film on the plurality of substrates.
• DCS dichlorosilane
• embodiment further includes flowing a third process gas comprising nitric oxide (NO) gas into the process chamber while flowing the first process gas and the second process gas; and reacting the oxide film with the third process gas to form a silicon oxynitride film on the substrate.
• a third process gas comprising nitric oxide (NO) gas
• FIG. 1 schematically shows a cross-sectional view of a batch processing system configured to process a plurality of substrates according to an embodiment of the invention
• FIG. 2 shows a process flow diagram of one embodiment of the method of depositing an oxide film on a substrate
• FIG. 3 shows a process flow diagram of one embodiment of the method of depositing an oxynitride film on a substrate
• FIG. 4 shows silicon oxide deposition rate as a function of DCS flow according to embodiments of the invention
• FIG. 5 shows wet etch rates of different silicon oxide films as a function of N 2 post- deposition heat-treating temperature according to embodiments of the invention.
• FIG. 6 shows capacitance-voltage curves for silicon oxide and silicon oxynitride films formed by embodiments of the invention.
• Embodiments of the invention provide a low-temperature deposition process for forming dielectric films for semiconductor devices.
• a method is provided for non-plasma CVD of silicon oxide films using dichlorosilane (DCS) and water vapor.
• DCS dichlorosilane
• a method is provided for non-plasma CVD of silicon oxynitride films using DCS, water vapor, and nitric oxide (NO) gas.
• Embodiments of the invention achieve high deposition rates of silicon dioxide and silicon oxynitride films with good material and electrical properties while utilizing lower deposition temperature than industry standard high-temperature oxide (HTO) processes that rely on the reaction of dichlorosilane (DCS) and nitrous oxide (N 2 0) on a substrate.
• HTO high-temperature oxide
• the inventors have realized that replacing a N2O oxidizer with a water vapor oxidizer, and optionally NO gas for forming silicon oxynitride films, allows for lowering the deposition temperature by greater than 100°C, greater than 200°, or even greater than 300°(e.g., up to 350°C) while providing silicon oxide films with good material properties that include low wet etch rates that are comparable to baseline HTO processes.
• This lowering of the deposition temperature provides the required lowering of the thermal budget needed for advanced integrated circuits, since a restricted thermal budget may not allow for increasing the substrate temperature and longer processing times may not be cost effective in high volume manufacturing of semiconductor devices.
• post-deposition thermal treatments at temperatures greater than the deposition temperature may optionally be performed to further improve the material and electrical properties of the silicon oxide and silicon oxynitride films.
• FIG. 1 shows a cross-sectional view of a batch processing system 10 having a process chamber 12 with a plurality of substrates 20 positioned within the process chamber 12.
• a batch processing system 10 is shown and described, the method is also applicable to single substrate processing where the substrates are processed one at a time.
• FIG. 2A and 2B depict process flow diagrams for forming silicon oxide and silicon oxynitride films, respectively, on the substrates 20 in FIG. 1.
• the plurality of substrates 20 are positioned in the process chamber 12.
• the substrates 20 may be positioned on a rotatable substrate holder 13.
• positioning or loading the substrates 20 within the batch processing system 10 may include exhausting the process chamber 12 through the exhaust port 15 and evacuating the process chamber 12 through a vacuum port 14 following insertion of the substrates 20.
• positioning the substrates 20 within the batch processing system 10 may also include purging the process chamber 12 with inert gas, such as nitrogen, to dilute or reduce the concentration of organic contaminants within the process chamber 12.
• the process chamber 12 is heated to a deposition temperature between 400°C and less than 650°C.
• a heating rate may be from a few degrees C per minute to 100 or more degrees C per minute.
• a first process gas containing water vapor is introduced into the process chamber 12 through an inlet port 16.
• the first process gas comprises water vapor but not a nitriding gas.
• a second process gas containing DCS and optionally a dilution gas is introduced into the process chamber 12 through an inlet port 17.
• a process gas pressure below 2Torr is established in the process chamber.
• oxygen from the water vapor reacts with the DCS in the gas phase and deposits a silicon oxide film onto each of the substrates 20.
• the substrates 20 may be positioned on a rotatable substrate holder 13. As one skilled in the art will observe, positioning or loading the substrates 20 within the batch processing system 10 may include exhausting the process chamber 12 through the exhaust port 15 and evacuating the process chamber 12 through a vacuum port 14 following insertion of the substrates 20. In addition, positioning the substrates 20 within the batch processing system 10 may also include purging the process chamber 12 with inert gas, such as nitrogen, to dilute or reduce the concentration of organic contaminants within the process chamber 12.
• inert gas such as nitrogen
• the process chamber 12 is then heated to a processing temperature between 400°C and less than 650°C.
• a heating rate may be from a few degrees C per minute to 100 or more degrees C per minute.
• a first process gas containing water vapor is introduced into the process chamber 12 through an inlet port 16.
• a second process gas containing DCS and optionally a dilution gas is introduced into the process chamber 12 through an inlet port 17.
• a third process gas containing NO and optionally a dilution gas is introduced into the process chamber.
• a process gas pressure below 2Torr is established in the process chamber.
• oxygen from the water vapor reacts with the DCS in the gas phase and the NO reacts such that nitrogen from the NO is incorporated into the silicon oxide film, thereby forming a silicon oxynitride film on each of the substrates 20.
• the processing ambients have a processing pressure.
• the inventors have realized that the processing pressure may be below 2Torr in order to deposit silicon oxide and silicon oxynitride films with good uniformity and the required material and electronic properties for semiconductor devices.
• the processing pressure can between 100 mTorr and less than 2 Torr, between 100 mTorr and 1 Torr, between 1 Torr and less than 2 Torr, between lTorr and 1.5 Torr, or between 1.5 Torr and less than 2 Torr.
• the deposition processes can utilize a deposition temperature between 400°C and less than 650°C, between 400°C and 450°C, between 400°C and 500°C, between 500°C and 550°C, between 500°C and 600°C, between 550°C and 600°C, between 550°C and less than 650°C, or between 600°C and less than 650°C.
• the processing pressure is set in conjunction with the processing temperature to control a deposition rate of the silicon oxide or silicon oxynitride film.
• the processing pressure and the flow rates of the gases may change at any time during the film deposition.
• set is not limited to a single act of setting the processing pressure, flow rates of gases, or processing temperature. Rather, set may refer to any number of settings or adjustments such that depositing a silicon oxide film or a silicon oxynitride film is in accordance with any quality standards either from internal controls, from industry, or determined by the customer.
• the flow rates of the first, second, and optional third process gas may range from 10 seem (standard cubic centimeters per minute) to 20 slm (standard liters per minute), 1 to 5000 seem for the NO nitriding gas, and lOOsccm to 20 slm for the diluting gas.
• the water vapor prior to flowing the first process gas containing water vapor into the process chamber 12, the water vapor is generated external to the process chamber 12, as shown in FIG. 1, by combustion of a hydrogen gas (H 2 ) and an oxygen gas (0 2 ).
• a hydrogen gas H 2
• an oxygen gas (0 2 ).
• One example of generating the first wet process gas is with a high-dilution pyrogenic torch 18, as depicted in FIG. 1, developed by Tokyo Electron Ltd., Nirasaki, Yamanashi, Japan.
• the high-dilution pyrogenic torch 18 combusts small flows of hydrogen gas and oxygen gas.
• the pyrogenic torch 18 thus generates the water vapor, i.e., water vapor in the form of steam, external to the process chamber 12.
• a diluting gas is used to dilute the first and second process gases in the processing ambient.
• the ratio of the concentration of the diluting gas to the concentration of the first and second process gases may influence the deposition rate of the silicon oxide or silicon oxynitride films. Therefore, the diluting gas may be used to control the silicon oxide film growth rate and the silicon oxynitride film growth rate.
• the diluting gas comprises nitrogen (N 2 ), as shown in FIG. 1.
• nitrogen N 2
• other non- reactive gases may be used, for example, argon (Ar).
• argon (Ar) argon
• FIG. 1 those skilled in the art will readily realize that a nitrogen diluting gas may be used to dilute the first process gas containing water vapor without flowing NO gas into the process chamber.
• the substrates 20 having the film thereon are heat-treated at a heat-treating temperature that is higher than the deposition temperature.
• heat-treating a silicon dioxide or silicon oxynitride film on the substrates 20 may modify the properties of the film, particularly the film's electrical properties and thus the electrical properties of a device containing the film.
• the processing ambient and the processing pressure may be modified.
• the process chamber 12 may be vacuum purged one or more times to remove the processing ambient containing the first, second, and optional third process gas and the diluting gas, if any, prior to heat-treating.
• a heat-treating gas may be introduced and a heat-treating temperature and a heat-treating pressure may be established within the process chamber 12, which may require raising or lowering the pressure from the deposition pressure.
• the substrates 20 having the silicon oxide or silicon oxynitride film thereon may be transferred to a different treatment system for heat-treating.
• the heat-treating pressure may have similar ranges as the deposition pressure.
• the heat-treating gas comprises at least one of nitrogen (N 2 ), nitric oxide (NO), nitrous oxide (N 2 0), oxygen (0 2 ), or water (H 2 0), or combinations thereof.
• FIG. 4 shows silicon oxide deposition rate as a function of DCS flow according to embodiments of the invention.
• the film deposition conditions included a H 2 gas flow of lOOsccm and an 0 2 gas flow rate of 100 seem through the pyrogenic torch 18, a water vapor generator, thus generating the water vapor.
• a N 2 dilution gas flow rate of 200sccm was used to dilute the first process gas containing the water vapor.
• a processing pressure of 0.2 Torr was established during deposition of the silicon oxide films and the deposition temperature was varied from 450°C to 600°C.
• the silicon oxide film thicknesses were less than about ⁇ .
• the DCS gas flow rate was varied from lOsccm to 20sccm.
• Fig. 4 shows that increasing the DCS flow rate resulted in increased silicon oxide deposition rates from about 3-4 A/min to about 9-10 A/min at deposition temperatures of 450°C and 500°C, and from 6A/min to about 11 A/min at 600°C. Furthermore, for comparison, Fig. 4 shows that the deposition rate of silicon oxide films is only about 2 A/min at a deposition temperature of 810°C using the conventional HTO process of reacting DCS with N 2 0 on the substrate surface and the deposition rate is
• FIG. 5 shows wet etch rates of different silicon oxide films as a function of N 2 post- deposition heat-treating temperature according to embodiments of the invention.
• Wet etch rates are a measure of a material quality of the silicon oxide films, where high quality silicon oxide films wet etch slower than low quality silicon oxide films.
• the deposited silicon oxide films were subsequently heat-treated for 1 hour in the (deposition) process chamber at different temperatures in the presence of N 2 gas at a processing pressure of 0.5 Torr.
• the silicon dioxide films were subjected to a wet etching process for 2.5 minutes in dilute HF (200:1, H 2 0:HF) and the etch rate normalized to the etch rate of baseline HTO silicon oxide films deposited at 800°C using a DCS gas flow rate of 50sccm and a N 2 0 gas flow rate of lOOsccm.
• FIG. 5 shows that for as-deposited silicon oxide films, higher deposition temperature or higher DCS gas flows resulted in higher wet etch rates. Further, the higher the post-deposition heat-treating temperature, the lower the wet etch rates for silicon oxide films deposited using DCS gas flow rates of lOsccm.
• the wet etch rate of a silicon oxide film deposited using a low DCS gas flow rate (lOsccm) at a substrate temperature of 600°C and subsequently heat-treated at a substrate temperature of 800°C in N 2 gas was less than that for the base line HTO silicon oxide films.
• FIG. 6 shows capacitance-voltage curves for silicon oxide and silicon oxynitride films formed by embodiments of the invention.
• the silicon oxide films were deposited using DCS and water vapor and the silicon oxynitride films were depositing by adding 50sccm and lOOsccm of NO gas to the DCS and water vapor process gases.
• the results in Table 1 and FIG. 6 illustrate that the addition of the NO gas increases the T ox , the deposition rate, the equivalent oxide thickness (EOT), and the dielectric constant (K).
• interface trap density (D3 ⁇ 4) may be reduced by a factor of approximately 100 from that of a baseline silicon oxide, i.e., lowered from approximately E12eV _1 cm ⁇ 2 to approximately E10eV _1 cm ⁇ 2 .
• Such a D3 ⁇ 4 reduction would provide a silicon oxynitride film with an interface that is relatively free of charge traps and as such may be advantageously used as a gate dielectric for metal oxide semiconductor field effect transistor (MOSFET) devices with great improvements in electron/hole mobility and peak channel drive currents.
• MOSFET metal oxide semiconductor field effect transistor
• NVM non- volatile memory
• D3 ⁇ 4 values indicate increasing potential for interface charge trapping and possible shift in MOSFET threshold voltage (Vth)
• Vth MOSFET threshold voltage
• the improvements in reliability for NVM applications are thought to greatly outweigh any disadvantages from D3 ⁇ 4 increases.
• the increased N concentration is thought to be helpful in binding more tightly loose (dangling) atomic bonds within the film.
• the increased N concentration increases the density of the film and results in increased resistance to electron bombardment at elevated voltages that are often used during semiconductor processing. Overall, the results show that, unlike when using prior art reactions of DCS and N 2 0, adding NO during film deposition using DCS and H 2 0, is effective for incorporating N into silicon oxide films to form silicon oxynitride films for semiconductor devices.

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• 2010
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