CN101203945A - Method of forming a high dielectric constant film and method of forming a semiconductor device - Google Patents
Method of forming a high dielectric constant film and method of forming a semiconductor device Download PDFInfo
- Publication number
- CN101203945A CN101203945A CNA2006800225808A CN200680022580A CN101203945A CN 101203945 A CN101203945 A CN 101203945A CN A2006800225808 A CNA2006800225808 A CN A2006800225808A CN 200680022580 A CN200680022580 A CN 200680022580A CN 101203945 A CN101203945 A CN 101203945A
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- CN
- China
- Prior art keywords
- dielectric constant
- high dielectric
- constant film
- film
- silicon
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000004065 semiconductor Substances 0.000 title claims description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 239000002210 silicon-based material Substances 0.000 claims abstract description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 37
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract 5
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- 239000010703 silicon Substances 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
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- 238000013517 stratification Methods 0.000 claims 1
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- GMMGOEVABABMBA-UHFFFAOYSA-N CC(C)C(C)(C)N[Hf] Chemical group CC(C)C(C)(C)N[Hf] GMMGOEVABABMBA-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
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- 239000000376 reactant Substances 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
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- 229910000077 silane Inorganic materials 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
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- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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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
- H01L21/0228—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
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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
- C23C16/401—Oxides containing silicon
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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
- H01L21/02142—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
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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
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- 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
- H01L21/02142—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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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
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- H01L21/02107—Forming insulating materials on a substrate
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- 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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- 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
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- 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
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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
- H01L21/02172—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
- H01L21/02189—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 zirconium, e.g. ZrO2
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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
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
- H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
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Abstract
The method for forming a high dielectric constant film metal silicate on a substrate by atomic layer deposition using the gas of a metal-containing compound and the gas of a silicon-containing compound represented by the general formula (I), wherein R<1>, R<2> and R<3> in the preceding general formula are each independently selected from the hydrogen atom, C1-3 alkyl, and N(R<6>)2 (wherein each of the plurality of R<6> groups is independently selected from the hydrogen atom, C1-3 alkyl, and Si(R<7> )3 (wherein each of the plurality of R<7> groups is independently selected from the hydrogen atom and C1-3 alkyl)); R<4>and R<5> are each independently selected from the hydrogen atom, C1-3 alkyl, and Si(R<8> )3 (wherein each of the plurality of R<8> groups is independently selected from the hydrogen atom, C1-3 alkyl, and NHSi(R<9> )3 (wherein each of the plurality of R<9> groups is independently selected from the hydrogen atom and C1-3 alkyl)); and the value of (the number of carbon atoms in the preceding general formula)/(number of silicon atoms in the preceding general formula) is no more than 7.
Description
Technical field
The present invention relates to a kind of by the method for ald formation high dielectric constant film and the method that forms semiconductor device.
Background technology
Along with the compact in size of large scale integrated circuit, need the thin gate dielectric film that increases day by day.Because the increase of leakage current, silicon oxide film of Shi Yonging and silicon nitride film are subjected to the restriction of the degree that their thickness can be lowered up to now, and to SiO
2The requirement that equivalence film thickness≤1.5nm produces inferior-0.1 μ m CMOS has been very big challenge.Thereby, proposed to have the high dielectric constant film (height-k film) of metal-oxide film, metal silicate films or the metal aluminate form of film of higher relative dielectric constant by use ratio silicon oxide film or silicon nitride film, and by utilizing the thick film of physics to suppress leakage current.
Recently occurred having the report of the metal silicate films of excellent electric performance for attempting using in a large number as these high dielectric constant films.Chemical vapor deposition and sputtering method are generally used for forming metal silicate films.
Yet under the situation of chemical vapor deposition, being formed under about 300 ℃ of metal silicate films undertaken by the low temperature thin film preparation procedure, the impurity (＞10 that the result is a large amount of
21Cm
-3) remain in the film as carbon and hydrogen, produce unacceptable film quality problem.And, because being made up of used parent material, film determines, therefore be created under the situation that does not change used parent material film and form unalterable problem.
On the other hand, under the situation of sputtering method, in the starting stage process that forms metal silicate films, in silicon substrate, produce destruction by radical type from for example argon gas.This causes forming thick boundary layer (＞about 1nm) at the interface at metal silicate films/silicon substrate, and it makes and is difficult to reduce film thickness.
The ald (hereinafter being abbreviated as ALD) that can form the gate dielectric film on the atomic layer basis has been described recently.Using ALD to form the gate dielectric film makes and can change used parent material and change film and form.The metal aluminate film has been widely used in the gate dielectric film that ALD-makes.For example patent documentation 1 has been described by being prepared as follows method and has been formed for example Al
2O
3High dielectric constant film, this preparation method comprises:
The first step is wherein carried out oxidation by oxidizing gas ozoniferous with silicon substrate;
Second step wherein with the already oxidised surface hydroxylation of silicon substrate, then was first reactant such as trimethyl aluminium (TMA) absorption thereon; With
The 3rd step is wherein with second reactant such as H
2O introduce and make its with the surface of oxidation on first reactant reaction of remnants.
Metal aluminate film such as these have been widely used as the gate dielectric film that ALD-makes.This is because the well known following fact of a specified duration: it is relatively easy to use TMA (aluminium source) to form film as source material by ALD.
Attempted making metal silicate films with excellent electric performance by ALD.If the metal silicate films that ALD makes can be used for semiconductor device, this can improve the reliability of element thus than use the metal aluminate film suppress the generation of leakage current biglyyer.In addition, owing to also do not form thick boundary layer at the interface at metal silicate films/silicon substrate, the thickness that therefore reduces metal silicate films will be an easy thing.
In this regard, patent documentation 3 has been described a kind of method that forms metal silicate films by ald.This method is used Hf ((C
2H
5) (CH
3) N)
4The containing metal compound of form and O (Si (CH
3)
2H)
2Or ((CH
3)
3Si)
2The silicon-containing compound of form.
[patent documentation 1]
Japanese unexamined open (not examining or open or A) number of patent application 2003-188171
[patent documentation 2]
Japanese unexamined open (not examining or open or A) number of patent application 2004-214304
[patent documentation 3]
Japanese unexamined open (not examining or open or A) number of patent application 2004-165668
Summary of the invention
The problem to be solved in the present invention
About the metal silicate films that forms by aforesaid art methods, film forms also insufficient and film on matrix formation sexual needs improve.In addition, when these films have been used for semiconductor device, component reliability, for example leakage current generating does not also have inevitable satisfactory.
The means of dealing with problems
The method that is used to form high dielectric constant film according to the present invention is used the gas of containing metal compound and the gas of the silicon-containing compound represented by following general formula forms the high dielectric constant film that comprises metal silicate on base material by ald:
Wherein
R in aforementioned formula
1, R
2And R
3Be selected from hydrogen atom, C independently of one another
1-3Alkyl and N (R
6)
2(wherein a plurality of R
6In the group each independently is selected from hydrogen atom, C
1-3Alkyl and Si (R
7)
3(wherein a plurality of R
7In the group each independently is selected from hydrogen atom and C
1-3Alkyl));
R
4And R
5Be selected from hydrogen atom, C independently of one another
1-3Alkyl and Si (R
8)
3(wherein a plurality of R
8In the group each independently is selected from hydrogen atom, C
1-3Alkyl and NHSi (R
9)
3(wherein a plurality of R
9In the group each independently is selected from hydrogen atom and C
1-3Alkyl)); With
The value of (carbon number in the aforementioned formula)/(the silicon atom number in the aforementioned formula) is not more than 7.
The silicon-containing compound that contains the Si-N key that uses aforementioned formula to represent in this film formation method forms high dielectric constant film.This produces improved formation property of film on matrix and improved component reliability.
The method that the present invention is used for producing the semiconductor devices comprises the steps:
On silicon substrate, form the high dielectric constant film that comprises metal silicate;
On aforementioned high dielectric constant film, form polysilicon membrane; With
Remove high dielectric constant film and polysilicon membrane formation gate electrode by selectivity,
The step of wherein aforementioned formation high dielectric constant film is undertaken by above-mentioned film-formation method.
Owing to use silicon-containing compound with the formation high dielectric constant film, so this method that is used for producing the semiconductor devices provides the impurity of reduction such as the concentration of carbon in high dielectric constant film with above-mentioned general formula that provides.This can provide again itself has the more semiconductor device of low-leakage current.In addition, the silicon-containing compound that contains the Si-N key by use forms high dielectric constant film and has improved film and form property.These features make can provide the semiconductor device with improved reliability.
The invention effect
The invention provides a kind of method that is used to form the high dielectric constant film that shows improved film formation property and improved component reliability.The present invention also provides a kind of method with semiconductor device that the high dielectric constant film that the leakage current that reduces and improved film form property is provided that is used to make.
Implement best mode of the present invention
Below with reference to accompanying drawing embodiment of the present invention are described.Structural element identical in institute's drawings attached has been given identical reference symbol in institute's drawings attached, it is described and suitably omits.
Fig. 1 is a sectional view, and it shows the mos transistor structure example as the semiconductor device of considering in the present embodiment.Fig. 2-the 4th, the cross section artwork, it shows the method for making this semiconductor device.P-channel MOS transistor example is taked in description subsequently.
In the semiconductor device as shown in Figure 1, n-well area 2 forms on p-type silicon substrate 1, and with p-channel MOS transistor-formation zone by be called shallow trench isolation from or the element isolation trench structure 4 of STI distribute.STI4 is that wherein silicon oxide film 6 is embedded in structure in the groove that forms on the surface of silicon substrate 1.By on the surface that forms the silicon substrate 1 in the zone at the p-channel MOS transistor with given sequence stack sull 16, high dielectric constant film 17 and polysilicon membrane 22 with the structure gate electrode.This high dielectric constant film 17 is by forming with given sequence stack first high dielectric constant film 18 and second high dielectric constant film 20.The sidewall 26 that has near sector crosssection forms in the gate electrode both sides.In addition, form in the silicon substrate 1 in p-channel MOS transistor-formation zone of elongated area 24 (wherein introducing the zone of p-type impurity) and source drain district 28 (wherein introducing the zone of p-type impurity), form the p-channel MOS transistor thus with high concentration with low concentration.Interlayer dielectric film 30 forms as coating on p-channel MOS transistor-formation zone, forms in the contact hole that contact layer 32 forms in interlayer dielectric film 30.Contact layer 32 is electrically connected with source electrode-drain region 28.
The following method that is used to form high dielectric constant film is used in the method for the present embodiment that is used for producing the semiconductor devices.
The method that is used to form high dielectric constant film in the present embodiment uses the gas of containing metal compound and the gas of the silicon-containing compound that following general formula is represented to form the high dielectric constant film that comprises metal silicate by ald on base material,
Wherein
R in aforementioned formula
1, R
2And R
3Be selected from hydrogen atom, C independently of one another
1-3Alkyl and N (R
6)
2(wherein a plurality of R
6In the group each independently is selected from hydrogen atom, C
1-3Alkyl and Si (R
7)
3(wherein a plurality of R
7In the group each independently is selected from hydrogen atom and C
1-3Alkyl));
R
4And R
5Be selected from hydrogen atom, C independently of one another
1-3Alkyl and Si (R
8)
3(wherein a plurality of R
8In the group each independently is selected from hydrogen atom, C
1-3Alkyl and NHSi (R
9)
3(wherein a plurality of R
9In the group each independently is selected from hydrogen atom and C
1-3Alkyl)); With
The value of (carbon number in the aforementioned formula)/(the silicon atom number in the aforementioned formula) is not more than 7.
Because use the silicon compound that contains the Si-N key with above-mentioned general formula to form high dielectric constant film, this film-formation method provides improved film formation property and improved component reliability.
The present embodiment uses the method that this method for preparing high dielectric constant film is used for producing the semiconductor devices to be described below with reference to Fig. 2 to 4.
The method that the present embodiment is used for producing the semiconductor devices can be undertaken by following step:
(1) wherein use aforementioned film build method on silicon substrate 1, to form the step (Fig. 2 (b)-3 (c)) of the high dielectric constant film 17 that comprises metal silicate;
(2) wherein on high dielectric constant film 17, form the step (Fig. 3 (d)) of polysilicon membrane 14; With
(3) wherein remove the step (Fig. 4 (e)-(h)) that high dielectric constant film 17 and polysilicon membrane 14 forms gate electrodes by selectivity.
The step (Fig. 2 (a)-(b)) that wherein forms silicon oxide film on the silicon substrate surface is carried out before also can forming the step of high dielectric constant film 17 therein.
At first, shown in Fig. 2 (a), n-well area 2 forms in p-type silicon substrate 1, and shallow trench also forms in the element isolated area of p-type silicon substrate 1.Then silicon oxide film 6 is embedded in the groove to form STI4.This silicon oxide film 6 can be for example by following program embedding: silicon oxide film 6 forms on the surface of silicon substrate 1 in the mode that is filled in the groove, for example eat-backs silicon oxide film 6 by chemico-mechanical polishing (CMP) then and allows silicon oxide film 6 stay in the groove simultaneously with the surface that exposes silicon substrate 1.
The surface of clean silicon base material 1 is also with rare hydrofluoric acid treatment (DHF) then, and afterwards that about 0.5nm-is thick silicon oxide film 8 forms on the surface of silicon substrate 1.On the surface of silicon oxide film 8, form first high dielectric constant film 10 (Fig. 2 (b)) then.The formation of silicon oxide film 8 makes can prevent that the metallic element in first high dielectric constant film 10 is diffused in the silicon substrate 1.
Provide first high dielectric constant film 10 by on silicon substrate 1, forming the high dielectric constant film that comprises metal silicate by ald.More specifically, in the ALD device, operate, be fed on the silicon substrate 1 and thereafter oxidizing gas be fed on the silicon substrate 1 and metal oxide is deposited on (first step) on the silicon substrate 1 by gas with the containing metal compound.Be fed on the silicon substrate by gas then and thereafter oxidizing gas be fed on the silicon substrate and silica is deposited to (second step) on the silicon substrate 1 silicon-containing compound.The repetition first step and second step make and form first high dielectric constant film 10 that comprises the metal silicate of being made up of metal, oxygen and silicon on the surfaces of silicon substrate 1.That is to say that first high dielectric constant film 10 forms by the sequential aggradation of metal oxide and silica.The thickness of first high dielectric constant film 10 can be 0.5nm-3nm.Oxidizing gas can for example be ozone or oxygen-containing gas.
Metallic element in the containing metal compound that is used to form first high dielectric constant film 10 can be that what to exemplify is hafnium (Hf), zirconium (Zr), tantalum (Ta), scandium (Sc), yttrium (Y), group of the lanthanides (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb) and lutetium (Lu), and can use and be selected from above-mentioned one or more.Preferred hafnium (Hf) or the zirconium (Zr) of using is as the metallic element in the containing metal compound in the present embodiment.That containing metal compound self can specifically exemplify is tetramethyl ethylamino hafnium (Hf (N (CH
3) (C
2H
5))
4), four dimethylamino hafniums (Hf (N (CH
3)
2)
4) and four diethylamino hafniums (Hf (N (C
2H
5)
2)
4).
Silicon-containing compound is represented by following general formula:
Wherein
R in aforementioned formula
1, R
2And R
3Be selected from hydrogen atom, C independently of one another
1-3Alkyl and N (R
6)
2(wherein a plurality of R
6In the group each independently is selected from hydrogen atom, C
1-3Alkyl and Si (R
7)
3(wherein a plurality of R
7In the group each independently is selected from hydrogen atom and C
1-3Alkyl));
R
4And R
5Be selected from hydrogen atom, C independently of one another
1-3Alkyl and Si (R
8)
3(wherein a plurality of R
8In the group each independently is selected from hydrogen atom, C
1-3Alkyl and NHSi (R
9)
3(wherein a plurality of R
9In the group each independently is selected from hydrogen atom and C
1-3Alkyl)); With
The value of (carbon number in the aforementioned formula)/(the silicon atom number in the aforementioned formula) is not more than 7.
In the defined silicon-containing compound of aforementioned formula, R wherein
1, R
2And R
3Be selected from hydrogen atom, methyl, N (CH independently of one another
3)
2And NHSi (CH
3)
3, and R
4And R
5Be selected from hydrogen atom, methyl, SiH independently of one another
3, Si (CH
3)
3And NHSi (CH
3)
3Silicon-containing compound be preferred the use.
Owing to be set at and be not more than 7 for the silicon-containing compound with aforementioned formula (the carbon number)/value of (silicon atom number), therefore can be reduced in impurity in the high dielectric constant film 17, as the concentration of carbon.In addition, because silicon-containing compound has the structure of Si-N key, therefore improved film formation property of high-k thin 17.As a result, being created in of leakage current suppressed in the semiconductor device with high dielectric constant film 17 and device reliability is improved.
That this silicon-containing compound can specifically exemplify is (SiH
3)
3N (three silicyl amine or TSA, fusing point=-106 ℃, boiling point=52 ℃), SiH
2(N (CH
3)
2)
2(bisdimethyl amino silane or BDMAS, fusing point=-104 ℃, boiling point=93 ℃), SiH (N (CH
3)
2)
3(three dimethylamino base silane or TDMAS, fusing point=-90 ℃, boiling point=145 ℃) and SiH
2(NHSi (CH
3)
3)
2(two (trimethyl silyl) amino silanes or BITS, fusing point=28 ℃, boiling point=40 ℃), and can use and be selected from aforementioned one or more selections.The use of these silicon-containing compounds provides even better result, and can effectively suppress the generation of leakage current, and the raising that can produce extra reliability.More preferably (SiH
3)
3N, SiH
2(N (CH
3)
2)
2And SiH (N (CH
3)
2)
3As silicon-containing compound, and preferred especially (SiH
3)
3N is used for silicon-containing compound.Because (SiH
3)
3N is carbon containing not, so it provides impurity in the good especially high dielectric constant film, and the reduction as the concentration of carbon causes strong especially leakage current to suppress.In addition, because it has the structure that comprises the Si-N key, it also provides the film formation property for the excellence of base material.Thereby (SiH
3)
3N (three silicyl amine or TSA) provides the balance of the excellence between drain current suppressing and better film formation property.
After forming, aforesaid first high dielectric constant film 10 can then carry out the densification of this first high dielectric constant film 10.This densification program for example can be used nitrogen or by the gas that provides in the nitrogen is provided very small amount of oxygen, and can be 1-60 second and carry out rapid thermal treatment by oblique change annealing under 700 ℃-1050 ℃ heat treatment temperature at heat treatment time.This densification program also can be by being that rapid thermal treatment is carried out in 0.3 millisecond-100 milliseconds hurried oblique change annealing at heat treatment time.
On first high dielectric constant film, 10 surfaces, form second high dielectric constant film 12 (Fig. 3 (c)) then.More specifically, form second high dielectric constant film 12 that comprises the metal silicate of forming by metal, oxygen and silicon by ald.Metallic element in second high dielectric constant film 12 is identical with formation first high dielectric constant film 10, especially preferably uses hafnium (Hf) or zirconium (Zr).Second high dielectric constant film 12 is so that (metallic element)/(ratio of metallic element+Si) is not more than 0.6 mode and forms.It is believed that the reaction (videing infra) between second high dielectric constant film 12 and polysilicon membrane 14 can be inhibited by this measure, and the generation of leakage current can be inhibited thus.Second high dielectric constant film 12 can form the thickness of about 0.5nm.
The metal silicate that this second high dielectric constant film 12 also can be made up of metal, oxygen, silicon and nitrogen.In the case, the peak concentration of nitrogen can be 10-30 atom % in second high dielectric constant film 12.When the peak value of nitrogen is worth less than this, the compactness of second high dielectric constant film 12 is with deficiency, and in the activation heat treatment process, can not prevent from the gate electrode forming process, to be introduced in the impurity in the polysilicon fully, in phosphorus or boron diffusion to the first high dielectric constant film 10.After second high dielectric constant film 12 has formed, with itself and first high dielectric constant film, the 10 the same densification of carrying out.
Second high dielectric constant film, 12 formation backs then form polysilicon membrane 14 on second high dielectric constant film, 12 surfaces and ion is injected into (Fig. 3 (d)) in the polysilicon membrane 14.Owing to form n-well area 2, in the embodiment that is considered, boron (B) ion injected.When forming the p-well area, ion injects phosphorus (P).
By form the photoresist film (not shown) on polysilicon membrane 14 surfaces, exposure gate electrode pattern also develops and forms the photoresist mask then.Make with photoresist mask carry out etching and obtain wherein silicon oxide film 16, first high dielectric constant film 18, second high dielectric constant film 20 and polysilicon membrane 22 with the gate electrode (Fig. 4 (e)) of given sequence stack as mask.Then remove the photoresist mask after this etching.Then, use gate electrode as mask, the ion that carries out low concentration on the surface of silicon substrate 1 injects to form the elongated area 24 of auto arrangement.In the embodiment of being considered, inject boron (B) at n-well area 2 intermediate ions.Ion injects arsenic (As) under the situation of p-well area.
Then silicon nitride film is formed the surface of the thickness of hope, and eat-back this silicon nitride film by anisotropic etching with covering silicon substrate 1.This silicon nitride film only is retained in sides of gate electrodes as a result, forms sidewall 26 (Fig. 4 (f)).
Use gate electrode and sidewall 26 to carry out ion then and inject, thus the source drain district 28 of the auto arrangement that forms on silicon substrate 1 surface as mask.In the embodiment of being considered, inject boron (B) at n-well area 2 intermediate ions.Ion injects arsenic (As) (Fig. 4 (g)) under the situation of p-well area.
After source drain district 28 forms, use tiltedly change annealing to deliver to rapid thermal treatment silicon substrate 1.Annealing be should tiltedly become and polysilicon membrane 22, elongated area 24 and source drain 28 activation made.Temperature in this activation heat treatment is hanged down 10 ℃ than the temperature of the densification behind formation first high dielectric constant film 10 and second high dielectric constant film 12 at least.The p-channel MOS transistor forms by abovementioned steps.Form then that interlayer dielectric film 30 covers silicon substrates 1 and electric conducting material is embedded in the contact hole of being opened in the interlayer dielectric film 30, make semiconductor device thus with mos transistor structure as shown in Figure 1 to be formed for being electrically connected the contact layer 32 of source area and drain region.
The advantageous effects of this embodiment is as described below.
The metal silicate films that provides by prior art ALD, for example to form the improvement of property be desirable to the film of metal silicate films on matrix that form of the silicon-containing compound of describing by patent documentation 3.Film on stromal surface formation property problem even also existence in SiH4 (single silane).
In view of such circumstances, the inventor has carried out concentrated research and has formed property with the film that improves the metal silicate films on the stromal surface, found that film on the stromal surface forms property and can improve effectively by the silicon-containing compound (silicon source) that use has an ad hoc structure.More specifically, the inventor finds to use the silicon-containing compound that contains the Si-N key can provide the excellent film on matrix of demonstration to form the semiconductor device of property and improved reliability.Film on the matrix form the improvement of property and in addition the inhibition of above-mentioned leakage current generating by use (SiH
3)
3N, SiH
2(N (CH
3)
2)
2Or SiH (N (CH
3)
2)
3Be confirmed, and special in using (SiH
3)
3The N proof has good balance.
In the present embodiment, make semiconductor device by using the silicon-containing compound that just has above-mentioned general formula on silicon substrate, to form high dielectric constant film.Therefore semiconductor device has impurity (as the carbon) level of reduction in high dielectric constant film, thus and the leakage current and the improved reliability that reduce.
So far be commonly used for the Si (OC of silicon-containing compound
2H
5)
4The value of (carbon number) that (tetraethoxysilane or TEOS) has/(silicon atom number) is 8.This causes the impurity (carbon) of high dielectric constant film middle and high concentration and therefore produces leakage current.
The value of (carbon number) that the silicon-containing compound that uses in the present embodiment in contrast, has/(silicon atom number) is not more than 7.This can reduce the impurity (carbon) in the high dielectric constant film effectively thereby concentration also can suppress leakage current generating.In above-mentioned silicon-containing compound, these effects are especially by using carbon-free (SiH
3)
3N (three silicyl amine (TSA)) is proved.
Although previous embodiments of the present invention is described with reference to the accompanying drawings, this is an example of the present invention, also can use the various structures except that this structure.
For example, high dielectric constant film 17 is described according to double-layer structure in the present embodiment, but it also can only need form one or more layers and thereby the stacked structure of three layers or multilayer.
In addition, high dielectric constant film 17 can form one deck, if high dielectric constant film (metallic element)/(metallic element+Si) ratio is not more than 0.6.
In addition, previous examples relates to high dielectric constant film 17 in silicon substrate 1 lip-deep formation, have silicon oxide film 16 therebetween, but high dielectric constant film 17 can form on the surface of silicon substrate 1 directly also.
Embodiment
The embodiment that following silicon-containing compound is used for providing below.
Silicon-containing compound
(SiH
3)
3N (three silicyl amine or TSA, fusing point=-106 ℃, boiling point=52 ℃)
SiH
2(N (CH
3)
2)
2(bisdimethyl amino silane or BDMAS, fusing point=-104 ℃, boiling point=93 ℃)
SiH (N (CH
3)
2)
3(three dimethylamino base silane or TDMAS, fusing point=-90 ℃, boiling point=145 ℃)
The vapor pressure curve of these silicon-containing compounds is reported in Fig. 5.Be widely used as the Si (OC of silicon-containing compound
2H
5)
4(tetraethoxysilane or TEOS) is also as the reference report.Fig. 5 shows that TSA, BDMAS and TDMAS have vapour pressure thereby the easily processing higher than TEOS.TSA especially provides lot of advantages, that is, it has high vapour pressure, can be by conventional cyclinder gas charging, and its also carbon containing not.
Test implementation example 1
SiO
2Relation between film thickness and the period uses TDMAS, BDMAS and TSA to examine as silicon-containing compound.This result reports in Fig. 6.Specifically, by being fed on the silicon substrate 1 in the permission silicon-containing compound inlet chamber and with it, afterwards ozone gas is introduced in this chamber, with SiO
2Be deposited on the surface of silicon substrate 1 and form silicon oxide film.This carries out under 275 ℃ base material temperature.It is that the process setting of the silicon oxide film of about 0.08nm is a circulation that formation has thickness.
When TDMAS is used as the silicon source,, interior chamber's pressure is remained on 5.0 holders for the film that guarantees about 0.08nm/ circulation forms speed.It is believed that this is owing to compare owing to have lower vapour pressure with other silicon source, has bigger difficulty so be adsorbed onto on the silicon substrate.On the other hand, when BDMAS was used as the silicon source, interior chamber's pressure remained on 2.0 holders and forms speed to obtain approximately identical with TDMAS film.Interior chamber's pressure with TSA remains on 0.5 holder to obtain approximately identical film formation speed.Thereby for the film that reaches the 0.08nm/ circulation forms speed, it is necessary that the pressure in each silicon source is controlled.
These results confirm to use TDMAS, BDMAS and TSA to provide excellent as silicon-containing compound and form property at the lip-deep film of silicon substrate.
Test implementation example 2
According to the method for above-mentioned embodiment, use tetramethyl ethylamino hafnium (Hf (N (CH
3) (C
2H
5))
4) as metallic compound and use TDMAS, BDMAS or TSA forms high dielectric constant film (Hf silicate thin film) as silicon-containing compound.Fig. 7 has reported Hf composition ratio (Hf/ (Hf+Si)) that change with Hf/ in the parent material (Hf+Si), in the Hf silicate thin film.Interior chamber's pressure is along with the parent material that uses changes, and TSA is 0.5 holder, and BDMAS is 2.0 holders, and TDMAS is 5.0 holders.Use 275 ℃ base material temperature.
Fig. 7 shows that the composition of Hf silicate thin film can very well control by Hf/ (Hf+Si) ratio of parent material, and it has confirmed that also Hf/ (Hf+Si) composition ratio of Hf silicate thin film can control in the wide region of 0-100%.In addition, confirmed owing to made SiO
2It is roughly the same for each silicon source that film forms speed, so the Hf/ in each silicon source (Hf+Si) ratio and Hf/ (Hf+Si) composition ratio are controlled on same level.
According to the method for above-mentioned embodiment, use tetramethyl ethylamino hafnium to make semiconductor device as silicon-containing compound as metallic compound and TDMAS.First high dielectric constant film 10 is that about 2nm is thick, and second high dielectric constant film 12 is that about 0.5nm is thick.Carbon (C) in the high dielectric constant film (Hf silicate thin film) 17 and hydrogen (H) concentration are measured by secondary ion microprobe spectrum (SIMS) analysis.Fig. 8 (a) has reported the CONCENTRATION DISTRIBUTION that enters into silicon substrate 1 from Hf silicate thin film surface.Fig. 8 (a) shows that the concentration of carbon in the Hf silicate thin film is about 3 * 10 for using TDMAS as the silicon source
20Cm
-3
As manufacturing semiconductor device as described in the embodiment 1, difference is in this case, uses BDMAS as silicon-containing compound.Fig. 8 (b) has reported the CONCENTRATION DISTRIBUTION that enters into silicon substrate 1 from Hf silicate thin film surface.Fig. 8 (b) shows that the concentration of carbon in the Hf silicate thin film is about 1 * 10 for using BDMAS
20Cm
-3
Embodiment 3
As manufacturing semiconductor device as described in the embodiment 1, difference is in this case, uses TSA as silicon-containing compound.Fig. 8 (c) has reported the CONCENTRATION DISTRIBUTION that enters into silicon substrate 1 from Hf silicate thin film surface.Fig. 8 (c) shows that the concentration of carbon in the Hf silicate thin film is about 3 * 10 for using TSA
19Cm
-3
These results prove and use TDMAS, BDMAS or TSA to provide impurity in the high dielectric constant film (Hf silicate thin film) than the obvious reduction of TEOS (as, carbon) concentration as silicon-containing compound.Therefore use these silicon-containing compounds on silicon substrate, to form the leakage current that high dielectric constant film can reduce semiconductor device.In addition, it shows that also the concentration of carbon in the high dielectric constant film can control by selecting these silicon-containing compounds.
Brief Description Of Drawings
Fig. 1 is the schematic sectional view by the semiconductor device of the method manufacturing of embodiment described herein.
Fig. 2 is the method for semiconductor device is made in explanation in an embodiment described herein cross section artwork.
Fig. 3 is the method for semiconductor device is made in explanation in an embodiment described herein cross section artwork.
Fig. 4 is the method for semiconductor device is made in explanation in an embodiment described herein cross section artwork.
Fig. 5 is the figure that shows the silicon-containing compound vapor pressure curve that uses among the embodiment.
Fig. 6 is presented at the figure that concerns between the film thickness and period under the situation that the silicon oxide film that wherein will form about 0.08nm film thickness is set at a circulation.
Fig. 7 is the figure that shows the relation between Hf/ (Hf+Si) composition ratio of Hf/ (Hf+Si) ratio of parent material and Hf silicate thin film.
Fig. 8 shows the carbon (C) in the Hf silicate thin film and the figure of hydrogen (H) CONCENTRATION DISTRIBUTION.
Reference symbol
1......... silicon substrate
2.........n-well area
4.........STI
6......... silicon oxide film
8......... silicon oxide film
10......... first high dielectric constant film
12......... second high dielectric constant film
14......... polysilicon membrane
16......... silicon oxide film
17......... high dielectric constant film
18......... first high dielectric constant film
20......... second high dielectric constant film
22......... polysilicon membrane
24......... elongated area
26......... sidewall
28......... source drain district
30......... interlayer dielectric film
32......... contact layer
Claims (12)
1. method that forms high dielectric constant film, the high dielectric constant film that wherein comprises metal silicate are used the gas of containing metal compound and the gas of the silicon-containing compound represented by following general formula forms on matrix by ald:
Wherein
R in aforementioned formula
1, R
2And R
3Be selected from hydrogen atom, C independently of one another
1-3Alkyl and N (R
6)
2(wherein a plurality of R
6In the group each independently is selected from hydrogen atom, C
1-3Alkyl and Si (R
7)
3(wherein a plurality of R
7In the group each independently is selected from hydrogen atom and C
1-3Alkyl));
R
4And R
5Be selected from hydrogen atom, C independently of one another
1-3Alkyl and Si (R
8)
3(wherein a plurality of R
8In the group each independently is selected from hydrogen atom, C
1-3Alkyl and NHSi (R
9)
3(wherein a plurality of R
9In the group each independently is selected from hydrogen atom and C
1-3Alkyl)); With
The value of (carbon number in the aforementioned formula)/(the silicon atom number in the aforementioned formula) is not more than 7.
2. a method of making semiconductor device comprises the steps:
On silicon substrate, form the high dielectric constant film that comprises metal silicate;
On aforesaid high dielectric constant film, form polysilicon membrane; With
Remove high dielectric constant film and polysilicon membrane formation gate electrode by selectivity,
The step of wherein aforementioned formation high dielectric constant film is undertaken by the film-formation method according to claim 1.
3. according to the method for the manufacturing semiconductor device of claim 2, the R in the aforementioned formula wherein
1, R2 and R3 be selected from hydrogen atom, methyl, N (CH independently of one another
3)
2And NHSi (CH
3)
3, R
4Be selected from hydrogen atom, methyl, SiH independently of one another with R5
3, Si (CH
3)
3And NHSi (CH
3)
3
4. according to the method for the manufacturing semiconductor device of claim 2 or 3, the compound that wherein has aforementioned formula is to be selected from by (SiH
3)
3N, SiH
2(N (CH
3)
2)
2, SiH (N (CH
3)
2)
3And SiH
2(NHSi (CH
3)
3)
2At least a in the group of forming.
5. according to the method for the manufacturing semiconductor device of claim 2 or 3, the compound that wherein has aforementioned formula is (SiH
3)
3N.
6. according to the method for the manufacturing semiconductor device of claim 2 or 3, the compound that wherein has aforementioned formula is SiH
2(N (CH
3)
2)
2
7. according to the method for the manufacturing semiconductor device of claim 2 or 3, the compound that wherein has aforementioned formula is SiH (N (CH
3)
2)
3
8. according to the method for each manufacturing semiconductor device among the claim 2-7, wherein the metal of high dielectric constant film/(composition ratio of metal+Si) is for being not more than 0.6 in the upper area at least of high dielectric constant film.
9. according to the method for each manufacturing semiconductor device among the claim 2-8, the step of wherein aforementioned formation high dielectric constant film comprises
By ald, on aforesaid silicon substrate, form the step of first high dielectric constant film that comprises metal silicate; With
On the surface of first high dielectric constant film, the metal that stratification has/(composition ratio of metal+Si) is not more than the step of 0.6 second high dielectric constant film.
10. according to the method for each manufacturing semiconductor device among the claim 2-9, wherein said metal comprises Hf or Zr.
11. according to the method for each manufacturing semiconductor device among the claim 2-10, wherein
The step that forms silicon oxide film on the silicon substrate surface before the step of aforementioned formation high dielectric constant film, carry out and
The step that forms high dielectric constant film is by ald, forms the step of the high dielectric constant film that comprises metal silicate on the lip-deep silicon oxide film of foregoing silicon substrate material.
12. according to the method for each manufacturing semiconductor device among the claim 2-10, wherein the step that forms high dielectric constant film by ald be on silicon substrate by repeating the step that following step forms the high dielectric constant film that comprises metal silicate:
Be fed to then oxidizing gas to be fed on the silicon substrate on the silicon substrate by gas metal oxide is deposited on the silicon substrate the containing metal compound; With
Be fed to then oxidizing gas to be fed on the silicon substrate on the silicon substrate by gas silica is deposited on the silicon substrate silicon-containing compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005180635A JP4554446B2 (en) | 2005-06-21 | 2005-06-21 | Manufacturing method of semiconductor device |
| JP180635/2005 | 2005-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101203945A true CN101203945A (en) | 2008-06-18 |
Family
ID=37022866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800225808A Pending CN101203945A (en) | 2005-06-21 | 2006-06-21 | Method of forming a high dielectric constant film and method of forming a semiconductor device |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1913629A1 (en) |
| JP (1) | JP4554446B2 (en) |
| KR (1) | KR20080038305A (en) |
| CN (1) | CN101203945A (en) |
| WO (1) | WO2006136584A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956695A (en) * | 2011-08-19 | 2013-03-06 | 台湾积体电路制造股份有限公司 | Semiconductor device having high-k gate dielectric layer and manufacturing method thereof |
| CN105849221A (en) * | 2013-09-27 | 2016-08-10 | 乔治洛德方法研究和开发液化空气有限公司 | Amine substituted trisilylamine and tridisilylamine compounds |
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| JP2006261434A (en) | 2005-03-17 | 2006-09-28 | L'air Liquide Sa Pour L'etude & L'exploitation Des Procede S Georges Claude | Method for forming silicon oxide film |
| JP5679622B2 (en) * | 2008-01-31 | 2015-03-04 | 株式会社東芝 | Insulating film and semiconductor device using the same |
| KR101377069B1 (en) | 2008-05-23 | 2014-03-24 | 삼성전자주식회사 | Semiconductor device and method of forming thereof |
| US8129555B2 (en) * | 2008-08-12 | 2012-03-06 | Air Products And Chemicals, Inc. | Precursors for depositing silicon-containing films and methods for making and using same |
| JP2012104808A (en) * | 2010-10-14 | 2012-05-31 | Dainippon Screen Mfg Co Ltd | Heat treatment apparatus and heat treatment method |
| JP2013084902A (en) * | 2011-09-26 | 2013-05-09 | Dainippon Screen Mfg Co Ltd | Heat treatment method and heat treatment apparatus |
| KR20150036122A (en) | 2012-07-20 | 2015-04-07 | 레르 리키드 쏘시에떼 아노님 뿌르 레뜌드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 | Organosilane precursors for ald/cvd silicon-containing film applications |
| US9382268B1 (en) | 2013-07-19 | 2016-07-05 | American Air Liquide, Inc. | Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications |
| TW201509799A (en) | 2013-07-19 | 2015-03-16 | Air Liquide | Hexacoordinate silicon-containing precursors for ALD/CVD silicon-containing film applications |
| US10570513B2 (en) | 2014-12-13 | 2020-02-25 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications and methods of using the same |
| US11124876B2 (en) | 2015-03-30 | 2021-09-21 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
| US9777025B2 (en) | 2015-03-30 | 2017-10-03 | L'Air Liquide, Société pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
| KR102581692B1 (en) | 2015-08-05 | 2023-09-22 | 도아고세이가부시키가이샤 | Carbon Analysis Methods |
| US10192734B2 (en) | 2016-12-11 | 2019-01-29 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploration des Procédés Georges Claude | Short inorganic trisilylamine-based polysilazanes for thin film deposition |
| WO2019188103A1 (en) * | 2018-03-29 | 2019-10-03 | 住友精化株式会社 | Aminosilane compound, and composition for silicon-containing film formation containing said aminosilane compound |
| WO2020131635A1 (en) * | 2018-12-21 | 2020-06-25 | K.K. Air Liquide Laboratories | PRECURSORS AND PROCESSES FOR DEPOSITION OF SI-CONTAINING FILMS USING ALD AT TEMPERATURE OF 550ºC OR HIGHER |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4693970B2 (en) * | 2000-09-14 | 2011-06-01 | 株式会社トリケミカル研究所 | Method for forming gate oxide film |
| US6391803B1 (en) * | 2001-06-20 | 2002-05-21 | Samsung Electronics Co., Ltd. | Method of forming silicon containing thin films by atomic layer deposition utilizing trisdimethylaminosilane |
| JP4007044B2 (en) * | 2002-04-19 | 2007-11-14 | ソニー株式会社 | Thin film formation method using atomic layer deposition |
| TW200408015A (en) * | 2002-08-18 | 2004-05-16 | Asml Us Inc | Atomic layer deposition of high K metal silicates |
| US20040198069A1 (en) * | 2003-04-04 | 2004-10-07 | Applied Materials, Inc. | Method for hafnium nitride deposition |
| JP2005064032A (en) * | 2003-08-12 | 2005-03-10 | Semiconductor Leading Edge Technologies Inc | Semiconductor device and its manufacturing method |
| JP4059183B2 (en) * | 2003-10-07 | 2008-03-12 | ソニー株式会社 | Insulator thin film manufacturing method |
| JP2005159316A (en) * | 2003-10-30 | 2005-06-16 | Tokyo Electron Ltd | Manufacturing method for semiconductor device, film-forming apparatus, and memory medium |
| JP2005191482A (en) * | 2003-12-26 | 2005-07-14 | Semiconductor Leading Edge Technologies Inc | Semiconductor device and its manufacturing method |
| JP2006016641A (en) * | 2004-06-30 | 2006-01-19 | L'air Liquide Sa Pour L'etude & L'exploitation Des Procede S Georges Claude | Method for producing metal silicon oxide, method for producing metal silicon oxynitride and method for producing silicon-doped metal nitride |
| US7098150B2 (en) * | 2004-03-05 | 2006-08-29 | Air Liquide America L.P. | Method for novel deposition of high-k MSiON dielectric films |
-
2005
- 2005-06-21 JP JP2005180635A patent/JP4554446B2/en not_active Expired - Fee Related
-
2006
- 2006-06-21 EP EP06777405A patent/EP1913629A1/en not_active Withdrawn
- 2006-06-21 KR KR1020087001550A patent/KR20080038305A/en not_active Application Discontinuation
- 2006-06-21 WO PCT/EP2006/063414 patent/WO2006136584A1/en not_active Application Discontinuation
- 2006-06-21 CN CNA2006800225808A patent/CN101203945A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956695A (en) * | 2011-08-19 | 2013-03-06 | 台湾积体电路制造股份有限公司 | Semiconductor device having high-k gate dielectric layer and manufacturing method thereof |
| US8987095B2 (en) | 2011-08-19 | 2015-03-24 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method of fabricating a carbon-free dielectric layer over a carbon-doped dielectric layer |
| US9385208B2 (en) | 2011-08-19 | 2016-07-05 | Taiwan Semiconductor Manufacturing Company, Ltd. | Semiconductor device having high-K gate dielectric layer |
| CN105849221A (en) * | 2013-09-27 | 2016-08-10 | 乔治洛德方法研究和开发液化空气有限公司 | Amine substituted trisilylamine and tridisilylamine compounds |
| CN105793270B (en) * | 2013-09-27 | 2019-09-27 | 乔治洛德方法研究和开发液化空气有限公司 | The method for being coupled the synthesizing amino silane in a manner of halogen-free by catalytic dehydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080038305A (en) | 2008-05-06 |
| WO2006136584A1 (en) | 2006-12-28 |
| EP1913629A1 (en) | 2008-04-23 |
| JP2007005365A (en) | 2007-01-11 |
| WO2006136584A8 (en) | 2008-03-13 |
| JP4554446B2 (en) | 2010-09-29 |
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