CN1689147A - Method for forming high dielectric film - Google Patents

Method for forming high dielectric film Download PDF

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Publication number
CN1689147A
CN1689147A CN03824483.7A CN03824483A CN1689147A CN 1689147 A CN1689147 A CN 1689147A CN 03824483 A CN03824483 A CN 03824483A CN 1689147 A CN1689147 A CN 1689147A
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forming
dielectric film
substrate
process space
film according
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杉田义博
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Fujitsu Ltd
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Fujitsu Ltd
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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
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • 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
    • H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
    • 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
    • H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate

Abstract

A method for forming a high-K dielectric film by the MOCVD method using an amine-based organic metal compound material, which comprises a step of supplying a raw material gas containing the amine-based organic metal compound material to a process space wherein a surface of a substrate to be treated is exposed, to thereby allow the surface of the substrate to be treated to adsorb the amine-based organic metal compound, a step of supplying a hydrogen gas to the surface of the substrate, and a step of supplying an oxidizing gas to the process space, to thereby form a high-K dielectric film on the surface of the substrate. The method allows the minimization of the amount of carbon remaining in the film.

Description

Method for forming high dielectric film
Technical Field
The present invention relates to the fabrication of semiconductor devices in general, and more particularly to the fabrication of semiconductor devices having high dielectric films.
Background
With the progress of miniaturization technology, it has become possible to manufacture ultra-fine and ultra-high-speed semiconductor devices having a gate length of 0.1 μm in a cutoff manner. In such an ultra-fine semiconductor device, in order to realize ultra-high speed operation, it is necessary to reduce the thickness of the gate insulating film to 1nm or less according to a scaling rule, and when such a very thin gate insulating film is used, a tunnel current flows through the semiconductor device, which causes a problem of an increase in gate leakage current.
In order to solve such a problem, it has been proposed to use, as a gate insulating film, a high-K dielectric film, which is a so-called high-K dielectric film, having an electrical film thickness in terms of a silicon oxide film, i.e., having a small oxide film thickness in terms of an oxide film, even if the physical film thickness is large, instead of the conventional silicon oxide film. ZrO can be used as such a high-K dielectric film2、HfO2、Al2O3A metal oxide film having a large dielectric constant and a large band gap, or ZrSiO4、HfSiO4And the like, metal silicide films, metal aluminate films, and the like.
In addition, such a high-K dielectric film is important for suppressing an increase in capacitor leakage current due to a tunnel current and securing a sufficient capacitance in a memory cell capacitor even in a DRAM cell having an ultra-fine memory cell capacitor with a small capacitance area.
Conventionally, such a high-K dielectric film is formed by an ALD (atomic layer deposition) method or an MOCVD method using an organic metal raw material. In the ALD method, organic metal material molecules are chemically adsorbed on the surface of a substrate to be processed, and a material molecule layer having a thickness of 1to 2 atomic layers chemically adsorbed thereby is oxidized by an oxidizing agent, so that a desired high-K dielectric layer is formed by repeating 1to 2 atomic layers.
As such an organometallic raw material, it is proposed to use, for example, tetrakis (dimethylamino) hafnium (Hf [ N (CH)]3)2]4) Tetra (diethylamino) hafnium (Hf [ N (CH)]2CH3)2]4) Tetra (dimethylamino) zirconium (Zr [ N (CH)]3)2]4) Tetra (diethylamino) zirconium (Zr (CH)2CH3)2)4) And the like.
However, these organometallic starting materials have a problem that a large amount of carbon remains in the high-K dielectric film to be formed because the starting material molecules contain organic functional groups.
In theory, Hf-N binding is weaker than N-C binding, so for example if H is used2O or O2、O3Etc. by reaction with an oxidizing agent
Or
And adsorbed Hf [ N (CH)3)2]4Molecular oxidation, presumably to form the desired HfO2A molecular layer.
That is, since one of the N-C bonds contained in the reactive organism of the oxidation reaction is stable as compared with the Hf-N bond in the raw material molecule, it is expected that HfO can be formed2The film without carbon remaining in the film.
However, as described above, in the high-K dielectric film formed using such an organometallic raw material, it is not avoided that carbon due to an organic functional group remains in the film, and a defect is formed in the film due to the remaining carbon. Further, when these residual carbons are oxidized and removed in a subsequent treatment step, a problem arises such as formation of voids in the film. Films containing such voids are not mechanically or chemically stable, and there is a problem that the reliability of a semiconductor device using a high-K dielectric film is lowered. In addition, the presence of voids lowers the dielectric constant of the high-K dielectric film.
In the studies of the inventors of the present invention which have been the basis of the present invention, the following facts have been found: for example, with Hf [ N (CH)3)2]4And oxygen as a raw material on the surface of the silicon substrateUpper make HfO2When the film is grown to a thickness of 3 to 5nm at a growth rate of several nanometers per minute at a substrate temperature of 200 to 550 ℃ and a process pressure of about 133Pa (1Torr), the concentration of residual carbon contained in the film is 1X 1020cm-3～1×1021cm-3。
On the other hand, in order to form a high-K dielectric film without containing residual carbon, it is proposed to use HfCl instead of an organometallic raw material4Or ZrCl4And the like. However, when such chloride is used as a raw material, chlorine remains in the obtained high-K dielectric film, and there is a risk thatproblems such as corrosion may occur in the vicinity of the high-K dielectric film.
On the other hand, it is known that amine-based organic metal materials have a characteristic of easily reacting with hydrogen to precipitate metal nitrides.
For example, in the presence of Hf [ N (CH)3)2]4In admixture with hydrogen, by reaction
(1)
Or
(2)
And precipitating metal Hf or HfN.
Since the organic functional group is very efficiently desorbed from the metal element in this reaction, it is considered that, when forming a high-K dielectric film using an amine-based organic metal material, the desorption of the organic functional group at the time of the metal element precipitation reaction on the surface of the substrate to be treated can be promoted by adding hydrogen gas to the material.
However, the reactions of the above formulae (1) and (2) are difficult to control and generally proceed very vigorously. Therefore, when hydrogen is simply added to the raw material gas, the problem of the large amount of metal particles generated as a result of the explosive reaction in the reaction vessel is inevitable.
Non-patent document 1 J.H.Lee, et al., IEDM pp.645-648, 2000
Non-patent document 2 Y.Kim, et al, IEDM pp.455-458, 2001
Non-patent document 3 y.oshita et al, j.crys.growth vol.233, p.292, 2001
Disclosure of Invention
Accordingly, a general object of the present invention is to provide a novel and useful method for forming a high-K dielectric film, which solves the above problems, and a method for manufacturing a semiconductor device using such a high-K dielectric film.
A more specific object of the present invention is to provide a method for forming a high-K dielectric film, which can minimize the amount of carbon remaining in the film when forming a high-K dielectric film by MOCVD using an amine-based organic metal material.
Another object of the present invention is to provide a method for forming a dielectric film using an amine-based organometallic starting material, the method comprising:
(A) supplying a source gas containing the amine-based organic metal molecules into a process space where a surface of a substrate to be processed is exposed;
(B) a step of removing the raw material gas from the process space after the step (a);
(C) supplying hydrogen gas to the surface of the substrate to be processed after the step (B);
(D) and (B) introducing an oxidizing gas into the process space after the step (B).
According to the present invention, in the step (a), the amine-based organometallic raw material molecules are adsorbed on the surface of the substrate to be treated, and in the step (B), after the amine-based organometallic raw material molecules are exhausted from the surface of the substrate to be treated, the step (C) is performed, whereby carbon is effectively removed from the film covering the surface of the substrate to be treated and containing the metal element in the organometallic raw material molecules, and a film containing substantially no carbon can be obtained. By subjecting the film thus obtained to oxidation treatment in the step (D), a desired dielectric film, particularly a high-K dielectric film, having a low carbon concentration and containing no halogen such as chlorine can be obtained. In the present invention, since the amine-based organic material gas which explosively reacts with hydrogen gas is removed from the process space on the surface of the substrate to be treated in the step (C), the problem of particles or the like does not occur.
Other objects and features of the present invention will become more apparent from the following detailed description of the present invention with reference to the accompanying drawings.
Drawings
Fig. 1 is a diagram showing the structure of an MOCVD apparatus used in the present invention;
FIG. 2 is a flowchart showing a film forming method according to embodiment 1 of the present invention;
FIG. 3 is a diagram illustrating a process sequence corresponding to the flow diagram of FIG. 2;
FIG. 4 is a view showing a process sequence of a film forming method according to embodiment 2 of the present invention;
FIG. 5 is a view showing a process sequence of a film forming method according to embodiment 3 of the present invention;
FIG. 6 is a schematic view of an MOCVD apparatus used in example 4 of the present invention;
FIG. 7 is a view showing a process sequence of a film forming method according to embodiment 4 of the present invention;
FIGS. 8A to 8D are views showing a manufacturing process of a high-speed semiconductor device according to embodiment 5 of the present invention;
fig. 9A to 9C are views showing a manufacturing process of a MOS capacitor according to embodiment 6 of the invention;
fig. 10 is a diagram showing the structure of an MOCVD apparatus according to embodiment 10 of the present invention.
Detailed Description
[ 1 st embodiment]
Fig. 1 shows a schematic configuration of an MOCVD apparatus 10 used in example 1 of the present invention.
Referring to fig. 1, an MOCVD apparatus 10 includes a processing container 11 that partitions a process space 11A and discharges gas from an exhaust port 11B, and a substrate holding table 12 that holds a substrate W to be processed is provided in the process space 11A. Although not shown, the substrate holding base 12 incorporates a heat source such as a resistance heater or a heating lamp. An exhaust line LV including an exhaust valve EV is connected to the exhaust port 11B.
Further, a shower head 13 made of quartz glass or the like is provided in the process space 11A so as to face the substrate W to be processed in the substrate holding table 12, and the shower heads 13 are connected to the line L together with nitrogen carrier gas1Supply of Hf [ N (CH)3)2]4(hereinafter referred to as TDEAH) and the likeMachine metal raw material gas, slave line L2Supply H2O or the like oxidizing gas, slave line L3Hydrogen gas is supplied.
More specifically, TEDAH is maintained in the source bottle 14 in the form of a liquid source material1The raw material bottle 141TEDAH slave line 15 in (1)1Bubbling (bubbling) by nitrogen gas supplied through the mass flow controller 15 a. The formed TEDAH gas is led from line 161The nitrogen carrier gas supplied together with the nitrogencarrier gas is supplied to the shower head 13 via a mass flow controller 16a through a valve 17a and a line L1.
Likewise, H2O in the raw material bottle 142Is maintained in the form of a liquid feed, i.e. water, by passage through a secondary line 152Bubbling through nitrogen gas supplied through the mass flow controller 15 b. H formed as a result2O gas, i.e. water vapour, from line 162Together with nitrogen carrier gas supplied via mass flow controller 16b through valve 17b and said line L2To said shower head 13.
Then, hydrogen gas passes through a line 15 from a gas collecting tank not shown3And a mass flow controller 15c, and a slave line 163The nitrogen carrier gas supplied via the mass flow controller 16c passes together through the valve 17c and the line L3To said shower head 13.
In addition, on the line L1、L2、L3In which are respectively provided with a valve LV1、LV2、LV3In said valve LV1Is provided with a breather valve VV on the upstream side1In said valve LV2Is provided with a breather valve VV on the upstream side2Also at said valve LV3Is provided with a breather valve VV on the upstream side3。
In this embodiment, using the MOCVD apparatus 10 of fig. 1, HfO is applied to the surface of the substrate W to be processed2The film is typically formed to a thickness of 2 to 5nm at a pressure of 133Pa (1Torr) and a substrate temperature of 200 to 550 ℃.
FIG. 2 shows HfO using the HfO of FIG. 12A flow chart of a film forming process.
Referring to FIG. 2, in initial step 1, valve LV1～LV3And closes the exhaust valve EV, and exhausts the process space 11A in the process container 11. In this step, the breather valve VV1～VV3All open, as a result of which said line L1～L3Is discharged to the outside of the system.
Next, in step S2, the exhaust valve EV and the vent valve VV are opened1Close and let valve LV1Open through said line L1A feed gas comprising TDEAH molecules is supplied to the process space 11A. As a result, TDEAH molecules contained in the raw material gas are chemisorbed on the surface of the substrate W to be processed, and a layer of the raw material molecules is formed so as to cover the substrate surface.
Next, in step S3, the exhaust valve EV and the vent valve VV are opened1～VV3Opening and closing the valve LV1～VV3Closed and the process space 11A is vented.
Further, in step S4, the exhaust valve EV and the vent valve VV2Close and let valve LV3The air conditioner is opened and then is opened,to connect the lines 153Through line 163Is supplied to the process space 11A in a state of being typically diluted to a concentration of 3%.
The reaction represented by the above formula (1) occurs between the hydrogen gas thus supplied and the TDEAH molecules adsorbed on the surface of the substrate W to be processed, and as a result, organic functional groups containing carbon are removed from the TDEAH molecules, and a layer made of metal Hf is formed so as to cover the surface of the substrate W to be processed.
Next, in step S5, the exhaust valve EV and the vent valve VV are used1～VV3All open and let the valve LV1～VV3Is closed, the process space 11A is exhausted, and the exhaust valve EV and the vent valve VV are exhausted instep S62Close and let valve LV2And (4) opening. As a result, the line L is led out of the process space 11A2Introduction of H2O gas, H introduced2O gas oxidizes Hf metal formed on the surface of the substrate W to convert it to HfO2And (3) a membrane.
After step S6, the process returns to step S1 to open the exhaust valve EV and the vent valve VV1～VV3And closing the valve LV1～VV3Whereby said process space 11A is evacuated.
Further, as shown in FIG. 3, by repeatedly performing the steps S1 to S6 in the stages I, II, …, HfO can be formed on the surface of the substrate W to be processed2The film is formed to a desired thickness of 2 to 5 nm. In which fig. 3 is a view showing a process sequence according to embodiment 1 of the present invention.
Referring to fig. 3, in the present embodiment, after the TDEAH raw material introduction step of step 2, the hydrogen gas introduction step of step 4 must be performed in the exhaust step of step 3, so that the residual TDEAH raw material is substantially completely removed from the process space 11A at the time when hydrogen gas is introduced, and the explosive reaction of hydrogen gas and residual TDEAH raw material and the problem of particles generated along with such reaction are effectively suppressed. The exhaust step of step 3 is sufficient to be performed for about 1 second. In the exhaust step of step 3, a purge gas such as nitrogen or Ar gas may be introduced into the process space 11A to improve the discharge efficiency of the residual TDEAH raw material.
Further, in the present invention, after the degassing step of step 3, in the desorption step of step 4, molecules of the TDEAH raw material adsorbed on the surface of the substrate W to be processed react with hydrogen gas to desorb organic functionalgroups, and therefore HfO obtained in step 6 is used as a substrate for a semiconductor device2The film does not contain residual carbon, and high-quality HfO with few defects can be obtained by using organic metal raw material2And (3) a membrane. The inventors of the present invention confirmed the HfO in experiments conducted in the studies underlying the present invention2The carbon concentration in the film is suppressed to 1 x 10 or less19cm-3. HfO thus formed2The film does not use chloride as a raw material, and therefore does not contain halogen such as chlorine.
In the adsorption step of step 2, the process of the present invention controls the TDEAH atomForming a molecular layer thickness TDEAH layer on the surface of the substrate W, and oxidizing the molecular layer TDEAH film to form a molecular layer thickness HfO in the oxidation step of step 62In the case of a film, the process of fig. 2 or 3 becomes a so-called ALD (atomic layer deposition) process. However, the present invention is not limited to the ALD process, and the step 2 may be performed to form the adsorption TDEAH layer having a thickness corresponding to a plurality of molecular layers on the substrate W to be processed.
In the present example, TDEAH was used as the amine-based organometallic raw material of Hf, but the present invention is not limited to such a specific organometallic raw material. For example, as an organometallic raw material of Hf, tetrakis (diethylamino) hafnium (Hf [ N (CH)]2CH3)2]4) And the like.
The present invention is not limited to HfO of an amine-based organometallic starting material using Hf2Formation of a film using zirconium tetrakis (dimethylamino) zirconium (Zr [ N (CH)]3)2]4) Tetra (diethylamino) zirconium (Zr [ N (CH)]2CH3)2]4) Formation of ZrO from amine-type organic metal raw materials of Zr2The film is also effective.
Furthermore, the present invention not only forms HfO2Film or ZrO2Film, also on HfSiO4Film or ZrSiO4Silicate film such as film, and HfAl2O5Or ZrAl2O5And the like, are also useful for forming an aluminate film. For example, as the organometallic raw material of Al, Al (CH) of the formula3)3Trimethylaluminum and the like are known, and SiCl of the formula is used as a raw material of Si4The tetrachlorosilane and the like are known.
In particular in the case of the formation of silicate or aluminate films, HfO is formed in stage I in the process sequence of fig. 32After the molecular layer, SiO is formed in stage II2Or Al2O3Thereby a desired compound film can be obtained.
In the manufacture of a p-channel MOS transistor, it is known that boron (B) contained in a gate electrode after a polysilicon gate electrode diffuses into a channel region in a subsequent heat treatment step, thereby causing a problem of fluctuation in threshold voltage. The most typical countermeasure to such a problem is to suppress the diffusion of B by containing nitrogen (N) in the gate oxide film. In the present invention using the amine-based raw material, nitrogen can be easily contained in the gate oxide film. That is, when introducing hydrogen gas, which is a characteristic of the present invention, about 1to 10% of ammonia (NH) is supplied3) Gas, which may be contained in the film at 1X 10 or more21cm-3Nitrogen (b) in the presence of nitrogen (b).
[ example 2]
FIG. 4 is a diagram showing HfO according to embodiment 2 of the present invention2Figure of process sequence for film formation.
Referring to fig. 4, in the present embodiment, the step 4 and the step 6 are replaced with each other, so that the oxidation step of step 6 is performed directly after the exhaust step of step 3, and the exhaust step of step 5 is performed after the oxidation step of step 6, and then the hydrogen introduction step of step 4 is performed.
In the process of fig. 4, in step 4, hydrogen molecules are adsorbed on HfO formed in the previous process2On the membrane, the remaining hydrogen molecules pass throughThe exhaust step in step 1 of the next stage II is removed from the process space 11A.
Therefore, in the step 2 of the stage II, when an amine-based organometallic starting material of Hf, such as TDEAH, is introduced into the process space 11A, HfO formed previously is introduced2When the TDEAH molecules are adsorbed on the film, the reaction (1) is carried out, and the organic functional groups are removed to precipitate metal Hf.
Therefore, after the TDEAH raw material remaining in the step 3 is removed from the process space 11A, the metal Hf layer composed of the metal Hf adsorbed in the step 6 is oxidized, whereby the concentration of carbon contained in the film is low, and HfO excellent in film quality can be obtained2And (3) a membrane.
In this example, as in the previous examples, the amine-based organic metal material used is not limited to TDEAH, and the film to be formed is not limited to HfO2And (3) a membrane.
[ example 3]
FIG. 5 is a diagram showing HfO according to embodiment 3 of the present invention2Figure of process sequence for film formation.
Referring to fig.5, in the present embodiment, the initial HfO shown in stage I2In the film forming process, the processes of step 1to step 6 are performed in the same order as in the case of the foregoing fig. 3, and in the next stage II, the hydrogen introducing process of step 4 is performed directly after the exhausting process of step 1, and the TDEAH introducing process of step 2 is performed after the exhausting process of step 3.
After the TDEAH introduction process of step 2, the exhaust process of step 5 is performed, and then the TDEAH introduction process of step 4 is performed.
As described above, in the present example, since the hydrogen gas introduction step is performed before and after the amine-based organometallic material introduction step, the organic functional group of the organometallic material molecule adsorbed on the substrate to be processed is reliably desorbed, and the obtained HfO can be reliably removed2The amount of carbon remaining in the high-K dielectric film of the like is minimized.
[ 4 th example]
Fig. 6 is a simplified schematic diagram of an MOCVD apparatus 10A used in the present embodimentFIG. 7 is a view showing HfO performed in the MOCVD apparatus of FIG. 62The film formation step.
Referring to fig. 6, MOCVD apparatus 10A has substantially the same configuration as MOCVD apparatus 10 of fig. 1, but differs in that only gas supply line L is used1And L2Omitting the gas supply line L3. At this time, in the present embodiment, on the line L1TDEAH is supplied as in the previous embodiment, but in line L2In addition to H2In addition to the O gas, hydrogen gas and a nitrogen carrier gas are supplied simultaneously. OrAt the line L2Hydrogen and oxygen are supplied. The following description is in the line L2Middle supply H2O gas and hydrogen.
Referring to FIG. 7, after the process space 11A is exhausted in the initial step 11, TDEAH feed gas is passed through the line L in step 121Is introduced into the process space and the TDEAH feed gas remaining in the process space 11A is removed by venting in step 13.
In the embodiment of fig. 7, then in step 14, from said line L2H is to be2O and hydrogen gas are introduced into the process space 11A together with the nitrogen carrier gas, and as a result, the TDEAH molecular layer covering the surface of the substrate W to be processed is oxidized in the process space 11A, and the organic functional groups are released.
Further, by repeating the steps 11 to 14 in the stages I, II, III, IV and …, HfO having a low carbon concentration is efficiently formed on the substrate W to be processed according to the present embodiment2And the like.
[ example 5]
Fig. 8A to 8D show a manufacturing process of an ultra high speed MOS transistor according to embodiment 5 of the present invention.
Referring to fig. 8A, a p-type well defined by an element isolation region 25B on a silicon substrate 21 is formed as an element region 21A, and the silicon substrate 21 is introduced as the substrate W to be processed into the MOCVD apparatus 10 of fig. 1 described above.
Furthermore, a silicon substrate 21 is formed of HfO by performing any one of the processes of fig. 2 to 72Or ZrO2、Al2O3A gate insulating film 22 made of a high-K dielectric film such as a metal oxide film, a silicate film, or an aluminate film.
In the step of fig. 8A, a polysilicon film 23 is uniformly formed on the gate insulating film22.
Next, in the step of fig. 8B, the polysilicon film 23 is patterned to form a polysilicon gate electrode pattern 23G, and P ion implantation is performed in the element region 21A using the gate electrode pattern 23G as a mask, thereby forming diffusion regions 21A and 21B on both sides of the gate electrode 23G in the element region 21A. In the step of fig. 8B, as a result of the patterning of the gate electrode pattern 23G, the high-K dielectric film 22 below the gate electrode pattern 23G is also patterned into a shape corresponding to the gate electrode 23G, thereby forming a gate insulating film pattern 22G.
Further, in the step of fig. 8C, sidewall insulating films 24A and 24B are formed on both side wall surfaces of the gate electrode pattern 23G, and P ion implantation is performed with an acceleration energy and a dose larger than those in the case of fig. 8B using the gate electrode pattern 23G and the sidewall insulating films 24A and 24B as masks, whereby n + -type diffusion regions 21C and 21d are formed outside the sidewall insulating films 24A and 24B in the element region 21A so as to partially overlap the diffusion regions 21A and 21B, respectively.
In the step of fig. 8D, a metal layer such as Co is deposited on the structure of fig. 8C, and after a short-time heat treatment, the metal layer is removed, thereby forming silicide regions 21S on the surfaces of the diffusion regions 21C and 21D. Such silicide regions 21S are also formed on the gate electrode 22G.
The MOS transistor thus formed uses HfO2And the like, since the gate insulating film 22G is made of a high-K dielectric film, even when the gate length is made finer to 0.1 μm or less, the gate insulating film has a sufficient physical film thickness, and the problem of an increase in gate leakage current can be avoided. Particularly in this embodiment, due to the gateSince the carbon concentration in the insulating film 22G is reduced, defects such as voids (void) are not generated, and a highly reliable film can be obtained.
[ 6 th example]
Fig. 9A to 9C show the manufacturing process of the MOS capacitor 40 according to embodiment 6 of the invention.
Referring to fig. 9A, an insulating film 42 made of a silicon oxide film or the like is formed on a silicon substrate 41 on which diffusion regions 41A are formed, and contact holes are formed in the insulating film 42 so as to expose the diffusion regions 41A.
In the step of fig. 9A, a polysilicon lower electrode 43 is formed on the insulating film 42 so as to be in contact with the diffusion region 41A through the contact hole, and the polysilicon lower electrode 43 is doped p-type or n-type in accordance with the conductivity type of the diffusion region 41A.
Next, in the step of fig. 9B, the silicon substrate 41 having the structure of fig. 9A is introduced into the processing container 11 of the MOCVD apparatus 10 of fig. 1 as the substrate W to be processed, and the steps described in fig. 2 and 3 or fig. 4 to 7 are performed, thereby forming HfO having a film thickness of 2 to 3nm on the surface of the polysilicon lower electrode 432And a capacitor insulating film 44 made of a high-K dielectric film.
Further, in the step of fig. 9C, a polysilicon upper electrode 45 is formed on the capacitor insulating film 44, thereby obtaining a MOS capacitor.
In the present embodiment, in the HfO used as the capacitor insulating film 442The concentration of impurities derived from organic metal materials such as carbon contained in the high-K dielectric film is suppressed, and a highly reliable film with a small leak current can be obtained. In particular, in the present example, voids generated in the film by oxidation of carbon are effectively suppressed by the carbon removal step, and as a result, electric field concentration in such voids can be avoided.
Further, in the present embodiment, the capacitor insulating film 44 is formed by adsorption and oxidation of the organic metal raw material gas, and therefore, even if the lower electrode 43 has a complicated shape, the capacitor insulating film 44 can be formed with a uniform film thickness.
With such a capacitor, a DRAM can be constituted.
[ 7 th example]
Fig. 10 shows the structure of an MOCVD apparatus 60 according to embodiment 7 of the present invention. In fig. 10, the same reference numerals are assigned to the previously described portions, and the description thereof is omitted.
Referring to fig. 10, the MOCVD apparatus 60 is an apparatus for batch processing, and has a processing container 61 that holds a plurality of substrates W to be processed in a process space 61A.
The processing chamber 61 is exhausted through an exhaust valve EV at an exhaust port 61B, and a heater 62 is provided outside the processing chamber 61.
In the batch type apparatus having such a configuration, as described above with reference to fig. 2 to 5, 6 and 7, the slave line L is switched1Supplied amine-based organic metal raw material such as TDEAH, and a line L2Supplied H2O or the like oxidizing agent, and slave line L3The hydrogen gas supplied can thereby avoid explosive reactions and at the same time effectively remove organic functional groups from the residual organometallic starting material, effectively reducing the carbon concentration in the high-K dielectric film formed.
The present invention has been described above based on preferred embodiments, but the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the spirit described in the scope of claims.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a film that can effectively remove carbon from a film covering a surface of a substrate to be treated and containing a metal element in an amine-based organometallic raw material molecule, by adsorbing the amine-based organometallic raw material molecule on the surface of the substrate to be treated, and then exhausting the amine-based organometallic raw material molecule from the surface of the substrate to be treated, and then allowing hydrogen gas to act on the adsorbed amine-based organometallic raw material molecule, thereby obtaining a film containing substantially no carbon. Here, by subjecting the film thus obtained to oxidation treatment, a desired dielectric film can be obtained. In the present invention, when the step of allowing the hydrogen gas to act is performed, the amine-based organic gas which explosively reacts with the hydrogen gas is removed from the process space on the surface of the substrate to be treated, and therefore, the problem of particles or the like does not occur.

Claims (17)

1. A method for forming a dielectric film using an amine-based organic metal material, comprising:
(A) supplying a source gas containing the amine-based organic metal molecules into a process space where a surface of a substrate to be processed is exposed;
(B) a step of removing the raw material gas from the process space after the step (a);
(C) supplying hydrogen gas to the surface of the substrate to be processed after the step (B);
(D) and (B) introducing an oxidizing gas into the process space after the step (B).
2. The method for forming a dielectric film according to claim 1, wherein the step (D) is performed after the step (C).
3. The method for forming a dielectric film according to claim 1, wherein the step (D) is performed simultaneously with the step (C).
4. The method for forming a dielectric film according to claim 1, wherein the step (D) is performed before the step (C).
5. The method for forming a dielectric film according to claim 1, wherein the steps (a) to (D) are repeatedly performed.
6. The method for forming a dielectric film according to claim 1, wherein, before the step (a), the steps of: (A1) supplying hydrogen to the process space; (A2) a step of removing hydrogen from the process space after the step (a 1).
7. The method for forming a dielectric film according to claim 6, wherein a step of introducing (A3) an oxidizing gas into the process space is performed before the step (A1).
8. The method for forming a dielectric film according to claim 6, wherein the steps (A2) to (D) are repeated.
9. The method for forming a dielectric film according to claim 1, wherein the step (a) covers the surface of the substrate to be processed to form a molecular layer of the organometallic starting material corresponding to a thickness of a plurality of molecular layers by the organometallic starting material molecules.
10. The method for forming a dielectric film according to claim 1, wherein the step (a) covers the surface of the substrate to be processed to form a molecular layer of the organometallic starting material corresponding to a thickness of a single molecular layer by the organometallic starting material molecules.
11. The method for forming a dielectric film according to claim 1, wherein the amine-based organic metal material contains any one of Hf, Zr, Si, Al, and Ti as a metal element.
12. The method for forming a dielectric film according to claim 1, wherein the dielectric film is formed of an oxide, a silicate, or an aluminate of any one metal element of Hf, Zr, and Al.
13. The method for forming a dielectric film according to claim 12, wherein the dielectric film is formed of HfO2Or ZrO2And (4) forming.
14. The method for forming a dielectric film according to claim 1, wherein the amine-based organic metal material contains a methylamino group, an ethylamino group, or a methylethylamino group.
15. The method for forming a dielectric film according to claim 14, wherein the amine-based organometallic raw material is tetrakis (dimethylamino) hafnium or tetrakis (dimethylamino) zirconium.
16. A method of manufacturing a semiconductor device, comprising:
forming a gate insulating film on a substrate;
forming a gate electrode on the gate insulating film;
a step of introducing an impurity element into the substrate with the gate electrode as a mask, wherein the step of forming the gate insulating film includes:
(A) supplying a source gas containing the amine-based organic metal molecules to a process space for holding the substrate;
(B) a step of removing the raw material gas from the process space after the step (a);
(C) supplying hydrogen gas to the surface of the substrate to be processed after the step (B);
(D) and (B) introducing an oxidizing gas into the process space after the step (B).
17. A method of manufacturing a capacitor, comprising:
forming a lower electrode on a substrate;
forming a capacitor insulating film on the lower electrode;
a step of forming an upper electrode on the capacitor insulating film, wherein the step of forming the capacitor insulating film includes:
(A) supplying a source gas containing the amine-based organic metal molecules to a process space for holding the substrate;
(B) a step of removing the raw material gas from the process space after the step (a);
(C) supplying hydrogen gas to the surface of the substrate to be processed after the step (B);
(D) and (B) introducing an oxidizing gas into the process space after the step (B).
CN03824483.7A 2003-04-17 2003-04-17 Method for forming high dielectric film Pending CN1689147A (en)

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