CN101373715A - Method for increasing energy band gap of aluminum oxide layer and method for manufacturing memory device - Google Patents
Method for increasing energy band gap of aluminum oxide layer and method for manufacturing memory device Download PDFInfo
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- CN101373715A CN101373715A CNA2008102133144A CN200810213314A CN101373715A CN 101373715 A CN101373715 A CN 101373715A CN A2008102133144 A CNA2008102133144 A CN A2008102133144A CN 200810213314 A CN200810213314 A CN 200810213314A CN 101373715 A CN101373715 A CN 101373715A
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- aluminium oxide
- amorphous nickel
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 398
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 234
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 117
- 229910052759 nickel Inorganic materials 0.000 claims description 117
- 239000011574 phosphorus Substances 0.000 claims description 117
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 117
- 238000010438 heat treatment Methods 0.000 claims description 73
- 238000002425 crystallisation Methods 0.000 claims description 46
- 230000008025 crystallization Effects 0.000 claims description 46
- 238000009279 wet oxidation reaction Methods 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 21
- 230000005641 tunneling Effects 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 238000000280 densification Methods 0.000 claims description 12
- 238000005468 ion implantation Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 74
- 238000005516 engineering process Methods 0.000 description 39
- 239000000758 substrate Substances 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 25
- 239000000463 material Substances 0.000 description 22
- 230000004888 barrier function Effects 0.000 description 17
- 238000012545 processing Methods 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004151 rapid thermal annealing Methods 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000619 electron energy-loss spectrum Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 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
- H01L21/02227—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
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D30/00—Field-effect transistors [FET]
- H10D30/01—Manufacture or treatment
- H10D30/021—Manufacture or treatment of FETs having insulated gates [IGFET]
- H10D30/0413—Manufacture or treatment of FETs having insulated gates [IGFET] of FETs having charge-trapping gate insulators, e.g. MNOS transistors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D30/00—Field-effect transistors [FET]
- H10D30/60—Insulated-gate field-effect transistors [IGFET]
- H10D30/69—IGFETs having charge trapping gate insulators, e.g. MNOS transistors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D30/00—Field-effect transistors [FET]
- H10D30/60—Insulated-gate field-effect transistors [IGFET]
- H10D30/69—IGFETs having charge trapping gate insulators, e.g. MNOS transistors
- H10D30/694—IGFETs having charge trapping gate insulators, e.g. MNOS transistors characterised by the shapes, relative sizes or dispositions of the gate electrodes
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- Manufacturing & Machinery (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
本发明提供了一种增大氧化铝层的能带隙的方法和一种制造电荷捕获存储装置的方法。即，本发明提供了具有增大的能带隙的结晶氧化铝层、包括结晶氧化铝层的电荷捕获存储装置和它们的制造方法。一种形成具有增大的能带隙的氧化铝层的方法包括以下步骤：在下膜上形成非晶氧化铝层；将氢(H)或羟基(OH)引入到非晶氧化铝层中；使包含H或OH的非晶氧化铝层结晶。
The present invention provides a method of increasing the energy band gap of an aluminum oxide layer and a method of manufacturing a charge trap memory device. That is, the present invention provides a crystalline alumina layer having an increased energy band gap, a charge trap memory device including the crystalline alumina layer, and methods of manufacturing them. A method of forming an aluminum oxide layer having an increased energy band gap includes the steps of: forming an amorphous aluminum oxide layer on a lower film; introducing hydrogen (H) or hydroxyl group (OH) into the amorphous aluminum oxide layer; The amorphous alumina layer containing H or OH crystallizes.
Description
Technical field
The present invention relates to the crystalline aluminum oxide layer, comprise the charge trap memory device and the manufacture method thereof of this crystalline aluminum oxide layer, more particularly, relate to the crystalline aluminum oxide layer of band gap, the charge trap memory device that comprises this crystalline aluminum oxide layer and manufacture method thereof with increase.
Background technology
The charge-trapping flash memory device of prior art (hereinafter, being called storage device) can comprise metal electrode, barrier oxide film, electric charge capture layer, tunnel oxide film and silicon base.The electric charge hold facility of the storage device of the prior art that these are exemplary can be determined by catch deeply energy, the thickness of tunnel oxide film and the electrical characteristics of barrier oxide film of electric charge capture layer.For example, the electrical characteristics of barrier oxide film comprise dielectric constant, band gap etc.
The electric charge hold facility of the band gap of barrier oxide film and storage device is closely related each other.For example, when the band gap of barrier oxide film was high relatively, the electric charge that is stored in the relatively small amount in the electric charge capture layer of storage device passed the barrier oxide film and escapes into metal electrode.Say that more generally along with the band gap increase of barrier oxide film, the charge leakage of passing the barrier oxide film from electric charge capture layer reduces.
The storage device of prior art can utilize pellumina as the barrier oxide film.The pellumina of prior art has the band gap of 6.5eV, and is that thermodynamics is metastable.Yet, because along with the raising of the integrated level of memory of future generation, the thickness of barrier oxide film can reduce, so the electric charge hold facility of the pellumina of prior art can be not enough to be used for developing storage device of future generation.If pellumina is too thin, then pellumina can be not enough to suppress the charge leakage of electric charge capture layer.
Summary of the invention
Example embodiment can provide more stable electric charge hold facility and/or have the barrier oxide film of bigger band gap.
Example embodiment relates to the method for making storage device, for example, relates to the method for the band gap that increases the amorphous nickel/phosphorus/aluminium oxide layer and utilizes this method to make the method for charge trap memory device.
Example embodiment relates to storage device, for example, relates to the alumina layer and the charge trap memory device that utilizes this alumina layer of the band gap with increase.
In order to improve the electric charge blocking capability as the crystalline aluminum oxide layer of electric charge barrier layer, example embodiment provides the method that increases the band gap of crystalline aluminum oxide layer.Example embodiment also provides the method for making the charge trap memory device with increase and more stable electric charge hold facility.
At least one example embodiment provides a kind of method that increases the band gap of alumina layer.According at least this method, can form the amorphous nickel/phosphorus/aluminium oxide layer at lower film, hydrogen (H) or hydroxyl (OH) can be introduced in the amorphous nickel/phosphorus/aluminium oxide layer.Can make the amorphous nickel/phosphorus/aluminium oxide layer crystallization of wherein having introduced H or OH.
At least one other example embodiment provides a kind of method that increases the band gap of alumina layer.According to this example embodiment at least, can form the amorphous nickel/phosphorus/aluminium oxide layer at lower film, hydrogen (H) or hydroxyl (OH) can be introduced in the amorphous nickel/phosphorus/aluminium oxide layer.Can carry out crystallization to the amorphous nickel/phosphorus/aluminium oxide layer of wherein having introduced H or OH.In single technical process, can form the amorphous nickel/phosphorus/aluminium oxide layer on the film down, and H or OH can introduced in the amorphous nickel/phosphorus/aluminium oxide layer.Can carry out this single technology, thereby by utilizing vapour deposition process or ald (ALD) method deposition to be in the alumina layer of amorphous state or crystalline state, and H or OH are introduced in this alumina layer.In this example embodiment, alumina layer can be crystalline aluminum oxide layer or the amorphous nickel/phosphorus/aluminium oxide layer that comprises H or OH.When alumina layer is when comprising the crystalline aluminum oxide layer of H or OH, can utilize Technology for Heating Processing to remove H or OH from the crystalline aluminum oxide layer that comprises H or OH.
At least one other example embodiment provides a kind of method of making charge trap memory device, and this charge trap memory device comprises tunneling membrane, electric charge capture layer, electric charge barrier layer and gate electrode.According to this example embodiment at least, can H or OH be introduced in the amorphous nickel/phosphorus/aluminium oxide layer, and make the amorphous nickel/phosphorus/aluminium oxide layer crystallization of wherein having introduced H or OH by forming the amorphous nickel/phosphorus/aluminium oxide layer at electric charge capture layer, form electric charge barrier layer.The alumina layer of crystallization can comprise the crystalline phase of band gap more than or equal to about 7.0eV.Can be with a kind of H or the OH of introducing in wet oxidation, ion implantation, the plasma doping method etc.
At least one other example embodiment provides a kind of method of making charge trap memory device.At least this example embodiment can be included in and form the crystalline aluminum oxide layer on the electric charge capture layer, and the band gap of this crystalline aluminum oxide layer is greater than the band gap relevant with the alumina layer with γ phase crystal structure.
At least one other example embodiment provides a kind of alumina layer structure with band gap of increase.This alumina layer structure can comprise the crystalline aluminum oxide layer, and the band gap of this crystalline aluminum oxide layer is greater than the band gap relevant with the alumina layer with γ phase crystal structure.
At least one other example embodiment provides a kind of charge trap memory device.According to this example embodiment at least, this charge trap memory device can comprise and is formed on suprabasil gate stack structure.This gate stack structure can comprise and is formed on suprabasil tunneling membrane, is formed on electric charge capture layer on the tunneling membrane, is formed on the alumina layer structure on the electric charge capture layer and is formed on gate electrode on the top surface of crystalline aluminum oxide layer structure.This alumina layer structure can comprise the crystalline aluminum oxide layer, and the band gap of this crystalline aluminum oxide layer is greater than the band gap relevant with the alumina layer with γ phase crystal structure.
According at least some example embodiment, when introducing H or OH in the amorphous nickel/phosphorus/aluminium oxide layer, the amorphous nickel/phosphorus/aluminium oxide layer can be in about temperature more than 800 ℃ (for example, between about 800 ℃ and about 850 ℃, comprise about 800 ℃ and about 850 ℃) under be transformed into the crystalline aluminum oxide layer that comprises H or OH.In this example, Technology for Heating Processing be can carry out, thereby H or OH removed at least in part from the crystalline aluminum oxide layer.
According at least some example embodiment, can utilize a kind of method in wet oxidation, ion implantation and the plasma doping method to inject H or OH.Can under atmospheric pressure and high temperature, carry out wet oxidation, perhaps can under high pressure and low temperature, carry out wet oxidation.
According at least some example embodiment, after being down on the film to form the amorphous nickel/phosphorus/aluminium oxide layer and introducing H or OH in the amorphous nickel/phosphorus/aluminium oxide layer, in the temperature range that can between about 800 ℃ and about 1300 ℃, (comprise about 800 ℃ and about 1300 ℃) alumina layer is carried out heat treatment, so that the alumina layer crystallization.In this example, can under the temperature (for example, being less than or equal to about 800 ℃) of the crystallization temperature that is lower than the amorphous nickel/phosphorus/aluminium oxide layer, carry out further heat treatment to the amorphous nickel/phosphorus/aluminium oxide layer.
According at least some example embodiment, can before or after wet oxidation, carry out densification process to the amorphous nickel/phosphorus/aluminium oxide layer, preferably, can be before wet oxidation (that is before, being injected into H or OH in the amorphous nickel/phosphorus/aluminium oxide layer) the amorphous nickel/phosphorus/aluminium oxide layer is carried out densification process.Can in single technology, carry out in the step of electric charge capture layer formation amorphous nickel/phosphorus/aluminium oxide layer with the step in H or the OH introducing amorphous nickel/phosphorus/aluminium oxide layer.When introducing H or OH in the amorphous nickel/phosphorus/aluminium oxide layer, the amorphous nickel/phosphorus/aluminium oxide layer can be more than or equal to about 800 ℃ temperature (for example, between about 800 ℃ and about 850 ℃, comprise about 800 ℃ and about 850 ℃) under be transformed into the crystalline aluminum oxide layer that comprises H or OH.In this example, Technology for Heating Processing be can carry out, thereby H or OH removed from the crystalline aluminum oxide layer.The step of the amorphous nickel/phosphorus/aluminium oxide layer being carried out crystallization comprises: in the temperature range that (comprises about 800 ℃ and about 1300 ℃) between about 800 ℃ and about 1300 ℃ alumina layer is carried out heat treatment.
When on electric charge capture layer, forming the amorphous nickel/phosphorus/aluminium oxide layer, after on electric charge capture layer, forming the amorphous nickel/phosphorus/aluminium oxide layer under the oxygen enrichment state, can introduce H.
According at least some example embodiment, can carry out densification process as mentioned above.Tunneling membrane can be silicon oxide film, silicon oxynitride film, silicon nitride film etc.
According at least some example embodiment, electric charge capture layer can comprise a plurality of nano dots, perhaps can be metal-doped high k oxides, for example, can comprise a plurality of aluminium oxide points.
Can be formed on the crystalline aluminum oxide layer that is used as electric charge barrier layer in this example embodiment at least by wet oxidation process and/or Technology for Heating Processing.In these technologies, the crystal structure of crystalline aluminum oxide layer can be transformed into κ mutually or the α phase mutually from γ.Therefore, according to this example embodiment at least, the band gap of crystalline aluminum oxide layer can be more than or equal to about 7.0eV.Therefore, the electric charge that can suppress to catch in the electric charge capture layer passes the crystalline aluminum oxide layer to gate electrode, thereby has improved the electric charge hold facility of storage device.
According at least some example embodiment, the band gap of crystalline aluminum oxide layer can be more than or equal to about 7.0eV.The crystalline aluminum oxide layer can have κ phase or α phase crystal structure.The crystalline aluminum oxide layer can comprise injection hydrogen (H) and hydroxyl (OH) at least a wherein.
According at least some example embodiment, the step that forms the crystalline aluminum oxide layer can comprise: forming the amorphous nickel/phosphorus/aluminium oxide layer on the film down, with at least a being injected in the amorphous nickel/phosphorus/aluminium oxide layer in hydrogen (H) and the hydroxyl (OH), make at least a amorphous nickel/phosphorus/aluminium oxide layer crystallization that comprises among H and the OH.The step of crystallization can comprise: the amorphous nickel/phosphorus/aluminium oxide layer is carried out first heat treatment.Can about 800 ℃ to about 1300 ℃ temperature range, be included under about 800 ℃ and about 1300 ℃, carry out first heat treatment.Can under the temperature of the crystallization temperature that is being lower than the amorphous nickel/phosphorus/aluminium oxide layer, carry out second heat treatment to the crystalline aluminum oxide layer.Can carry out the step that makes the crystallization of amorphous nickel/phosphorus/aluminium oxide layer, carry out simultaneously the step with at least a injection amorphous nickel/phosphorus/aluminium oxide layer among H and the OH.
According at least some example embodiment, can form tunneling membrane in substrate, can form electric charge capture layer at tunneling membrane.Can form gate electrode at the top surface of crystalline aluminum oxide structure.Tunneling membrane, electric charge capture layer, crystalline aluminum oxide layer and gate electrode can form gate stack structure.
According at least some example embodiment, can utilize gate stack structure as first mask first conductive impurity to be injected substrate, thereby in substrate, form first impurity range and second impurity range.Can on each side of gate stack structure, form the grid separator.Can utilize gate stack structure and grid separator as second mask second conductive impurity to be injected in the part of first impurity range and second impurity range.Can inject second conductive impurity, make in the win impurity range and second impurity range each comprise first with first degree of depth and second portion with second degree of depth.First degree of depth can be greater than second degree of depth.The grid separator can cover the second portion of first impurity range and second impurity range.
According at least some example embodiment, the second portion of first impurity range and second impurity range can be formed on its of substrate and be formed with in the part of grid separator.The surface of the part of the second portion that wherein is formed with first impurity range and second impurity range of substrate can be covered fully by grid separator and gate stack structure.
At least one other example embodiment provides a kind of method of making charge trap memory device.This charge trap memory device can comprise the gate stack that is formed by tunneling membrane, electric charge capture layer, α phase crystalline aluminum oxide layer and gate electrode, wherein, each in tunneling membrane, electric charge capture layer, α phase crystalline aluminum oxide layer and the gate electrode can sequentially be stacked in the substrate.According to this example embodiment at least, can form the amorphous nickel/phosphorus/aluminium oxide layer at electric charge capture layer.Can form metal level at the amorphous nickel/phosphorus/aluminium oxide layer, the similar or basic simlarity of space lattice of the space lattice of this metal level and α phase crystalline aluminum oxide layer.By the resulting structures that comprises this metal level is carried out heat treatment, can make the amorphous nickel/phosphorus/aluminium oxide layer be transformed into α phase crystalline aluminum oxide layer.
According at least some example embodiment, the step that makes the amorphous nickel/phosphorus/aluminium oxide layer be transformed into α phase crystalline aluminum oxide layer also can comprise: form mask on metal level; Etching sequentially is formed on metal level, amorphous nickel/phosphorus/aluminium oxide layer, electric charge capture layer and the tunneling membrane around the mask; The resulting structures that comprises metal level is carried out heat treatment.Described mask can limit the zone that can form gate stack.
According at least some example embodiment, make after the amorphous nickel/phosphorus/aluminium oxide layer is transformed into α phase crystalline aluminum oxide layer, this method also can comprise: form mask at metal level; Sequentially etching is formed on metal level, α phase crystalline aluminum oxide layer, electric charge capture layer and the tunneling membrane around the mask; Remove mask.Described mask can limit the zone that will form gate stack.After removing mask, can carry out heat treatment to the resulting structures that comprises metal level.Can be by for example TiCN layer, Rh
2O
3Layer, crystal orientation are a kind of formation metal level in the Ru layer of (0001).When metal level is Rh
2O
3During layer, can also carry out be used to making metal level be transformed into the heat treatment of conductive layer.Can (be included under about 1000 ℃ and about 1300 ℃) under normal pressure and in the temperature range between about 1000 ℃ to about 1300 ℃, carry out described heat treatment.
Description of drawings
To describe example embodiment in detail about accompanying drawing, in the accompanying drawings:
Fig. 1 to Fig. 9 is the cutaway view that illustrates according to the method for the manufacturing charge trap memory device of example embodiment;
Figure 10 be illustrate according to experimental example to Al
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map wherein, obtains this Al by carrying out heat treatment after the execution wet oxidation under relatively high pressure and relative low temperature
2O
3Layer;
Figure 11 is the Al that illustrates the x x ray diffraction analysis x result with Figure 10
2O
3The result's that the reflection electron-energy-loss spectrum (REELS) that layer is carried out is analyzed image;
Figure 12 be illustrate according to experimental example to Al
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map wherein, obtains this Al by carrying out heat treatment after the execution wet oxidation under atmospheric pressure and relative high temperature
2O
3Layer;
Figure 13 is the Al that illustrates the x x ray diffraction analysis x result with Figure 12
2O
3The result's that the REELS that layer is carried out analyzes image;
Figure 14 be illustrate according to experimental example to crystalline A l
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map, wherein, by to amorphous Al
2O
3Layer is only carried out the heat treatment under 1100 ℃ and is not carried out wet oxidation and obtain this crystalline A l
2O
3Layer;
Figure 15 is the Al that illustrates the x x ray diffraction analysis x result with Figure 14
2O
3The result's that the REELS that layer is carried out analyzes image;
Figure 16 to Figure 22 is the cutaway view that illustrates according to the method for the manufacturing charge trap memory device of example embodiment.
Embodiment
Describe various example embodiment more fully now with reference to accompanying drawing, some example embodiment have been shown in the accompanying drawing.In the accompanying drawings, for the sake of clarity, exaggerated the thickness in layer and zone.
The example embodiment of detailed illustrating property is here disclosed.Yet, in order to describe the purpose of example embodiment, on the specific structure disclosed herein and the details on the function only be representational.Yet, can implement the present invention with the form of many replaceabilities, and the present invention should not be interpreted as only limiting to example embodiment set forth herein.
Therefore,, show the embodiment of example embodiment in the accompanying drawings by the mode of example, and will describe the embodiment of example embodiment here in detail though example embodiment can have various modifications and selectable form.It should be understood, however, that intention does not make example embodiment be confined to disclosed concrete form, but opposite, example embodiment falls into all modifications, equivalent and alternative in the scope of the invention with covering.In the whole description of accompanying drawing, identical label represents identical element.
Can be used for describing different elements here though it should be understood that term " first ", " second " etc., these elements should not be subjected to the restriction of these terms.These terms only are used for an element and the difference of another element are come.For example, under the situation of the scope that does not break away from example embodiment, first element can be called as second element, and similarly, second element can be called as first element.As used herein, term " and/or " comprise the combination in any of one or more relevant Listed Items and all combinations.
It should be understood that when element or layer to be known as " being formed on " another element or layer when upper, this element or layer can be formed on another element or the layer directly or indirectly.That is, for example, can there be intermediary element or intermediate layer.On the contrary, when element or layer were known as " being formed directly into " another element or layer when upper, there are not intermediary element or intermediate layer.Should explain in an identical manner other word of being used to describe the relation between element or the layer (for example " and ... between " and " directly exist ... between ", " with ... adjacent " and " with ... direct neighbor " etc.).
Term used herein is only in order to describe the purpose of specific embodiment, and is not intended to limit example embodiment.As used herein, unless context points out clearly that in addition otherwise singulative also is intended to comprise plural form.It should also be understood that, when using term " to comprise " here and/or when " comprising ", illustrate to have described feature, integral body, step, operation, element and/or assembly, but do not get rid of existence or add one or more further features, integral body, step, operation, element, assembly and/or their group.In the accompanying drawings, for the sake of clarity, exaggerated the thickness in layer and zone.
Now, with the method (hereinafter, being called manufacturing method according to the invention) of describing according to the manufacturing charge trap memory device of example embodiment.Will with the method for coming together according to the manufacture method of example embodiment to describe according to the increase band gap of example embodiment.
To example embodiment be described about amorphous nickel/phosphorus/aluminium oxide layer and crystalline aluminum oxide layer.Yet, can utilize example embodiment in conjunction with the material that is different from aluminium, the described material that is different from aluminium for example is aluminium alloy or other metal with similar or similar substantially material character.
With reference to Fig. 1, can form (for example, sequentially forming) tunneling membrane 16, electric charge capture layer 18 and amorphous nickel/phosphorus/aluminium oxide layer 20a in substrate 10.Substrate 10 can be the semiconductor-based end, for example p type silicon base etc.
With reference to Fig. 2, can or comprise OH with hydrogen (H) and be incorporated among the amorphous nickel/phosphorus/aluminium oxide layer 20a, thereby form amorphous nickel/phosphorus/aluminium oxide layer 20b in conjunction with the hydroxyl (OH) of (OH coupling).Amorphous nickel/phosphorus/aluminium oxide layer 20b can be the amorphous nickel/phosphorus/aluminium oxide layer that comprises hydrogen (H) or contain the hydroxyl (OH) of OH combination.Hereinafter, amorphous nickel/phosphorus/aluminium oxide layer 20b will be called as OH material layer 20b, and the hydroxyl that comprises the OH combination will be called as " OH ".
According at least one example embodiment, can utilize such as wet oxidation etc. H or OH to be incorporated into to form OH material layer 20b among the amorphous nickel/phosphorus/aluminium oxide layer 20a.Can under temperature and pressure given or expectation, for example carry out wet oxidation in the vapor atmosphere.Wet oxidation can comprise heat treatment, wherein, under high relatively temperature and atmospheric pressure, carry out described heat treatment, perhaps (for example in low relatively temperature, between about 100 ℃ and about 450 ℃, comprise about 100 ℃ with about 450 ℃) carry out described heat treatment down with relative high pressure (for example,, comprising about 5atm and about 60atm) at about 5atm with approximately between the 60atm.The temperature of wet oxidation can according to or change based on the composition of the electric charge capture layer 18 that is formed on amorphous nickel/phosphorus/aluminium oxide layer 20a below.For example, when electric charge capture layer 18 is silicon nitride (SiN) film, carry out wet oxidation in the temperature range that can between about 500 ℃ to about 1000 ℃, (comprise about 500 ℃ and about 1000 ℃).
Wet oxidation process can increase H combination (H coupling) or the OH combination among the amorphous nickel/phosphorus/aluminium oxide layer 20a, thereby forms OH material layer 20b.
Replace wet oxidation, can utilize a kind of method in ion implantation, plasma doping method, the furnace treatment logos etc. that H or OH are incorporated into (thereby forming OH material layer 20b) among the amorphous nickel/phosphorus/aluminium oxide layer 20a.When utilizing ion implantation or plasma doping method to form OH material layer 20b, can in oxygen atmosphere or similar atmosphere, carry out Technology for Heating Processing to amorphous nickel/phosphorus/aluminium oxide layer 20a.Yet, when amorphous nickel/phosphorus/aluminium oxide layer 20a is amorphous oxygen-rich oxide aluminium lamination, can omit oxygen atmosphere heat treatment.
According at least some example embodiment, before or after wet oxidation, can carry out densification process to amorphous nickel/phosphorus/aluminium oxide layer 20a.In one embodiment, can before wet oxidation process, carry out densification process, for example, can carry out densification process with H or OH injection or before being incorporated into amorphous nickel/phosphorus/aluminium oxide layer 20a.
With reference to Fig. 3 and Fig. 4, can form crystalline aluminum oxide layer 20 by making OH material layer 20b crystallization.Can make OH material layer 20b crystallization by the resulting structures that comprises OH material layer 20b is carried out Technology for Heating Processing.Described Technology for Heating Processing can be carried out one or many (for example twice) at least.The crystalline texture of crystalline aluminum oxide layer 20 can be κ phase or α phase structure, but is not the γ phase structure.Crystalline aluminum oxide layer 20 can be used as the electric charge inhibition or work is come on the barrier layer.
Can be in given temperature (for example, between about 800 ℃ and about 1300 ℃, comprising about 800 ℃ and about 1300 ℃) the described Technology for Heating Processing of lower execution.When the crystalline aluminum oxide layer 20 that forms as shown in Figure 4, by under relatively high temperature, carrying out a heat treatment, can remove at least in part the H or the OH that comprise among the OH material layer 20b.Although can remove the H that is introduced among the amorphous nickel/phosphorus/aluminium oxide layer 20a or the part of OH, crystalline aluminum oxide layer 20 still can comprise H or OH.
In Technology for Heating Processing being carried out twice example embodiment, can carry out first Technology for Heating Processing, thereby remove at least in part H or OH from OH material layer 20b.Can under the temperature of the crystallization temperature that is lower than OH material layer 20b, carry out first Technology for Heating Processing.After first heat treatment, can be in relatively high temperature (for example, between about 800 ℃ and about 1300 ℃, comprising about 800 ℃ and about 1300 ℃) for the second time heat treatment of lower execution.
According to example embodiment, the H combination that exists among the OH material layer 20b or OH reduce the required formation energy of crystallization simultaneously in conjunction with helping (or auxiliary) to produce nucleus.Therefore, when H or OH being injected or (for example being incorporated into amorphous nickel/phosphorus/aluminium oxide layer 20a, utilize a kind of method in wet oxidation, ion implantation, the plasma doping method that H or OH are injected or be incorporated into amorphous nickel/phosphorus/aluminium oxide layer 20a) and when carrying out heat treatment subsequently, amorphous nickel/phosphorus/aluminium oxide layer 20a can be transformed into crystalline aluminum oxide layer 20, crystalline aluminum oxide layer 20 has κ phase or α phase structure, but is not the γ phase structure.Therefore, the band gap of the crystalline aluminum oxide layer 20 of gained can be more than or equal to about 7.0eV.
In at least one other example embodiment, can in single technology, carry out the formation of amorphous nickel/phosphorus/aluminium oxide layer 20a and the wet oxidation of amorphous nickel/phosphorus/aluminium oxide layer 20a.For example, utilizing when for example vapour deposition process, ald (ALD) method wait aluminum oxide layer, H or OH can be incorporated in the alumina layer.In this example, can form the alumina layer that comprises H or OH with amorphous state or crystalline state.
If form the alumina layer that comprises H or OH with crystalline state, then can carry out Technology for Heating Processing, thereby remove at least in part H or OH from the crystalline aluminum oxide layer.This Technology for Heating Processing can be used for making the Technology for Heating Processing of amorphous nickel/phosphorus/aluminium oxide layer 20a crystallization identical or basic identical.
If with the fault-tolerant alumina layer, then when introducing H or OH, the amorphous nickel/phosphorus/aluminium oxide layer can be transformed into the crystalline aluminum oxide layer that comprises H or OH.Transformation to the crystalline aluminum oxide layer can occur in more than or equal under about 800 ℃ temperature (for example between about 800 ℃ and about 850 ℃, comprising about 800 ℃ and about 850 ℃).In this example, can utilize Technology for Heating Processing (for example, making the Technology for Heating Processing of amorphous nickel/phosphorus/aluminium oxide layer 20a crystallization) to remove (for example, remove at least in part or remove fully) H or OH from the crystalline aluminum oxide layer that comprises H or OH.
With reference to Fig. 5, can form gate electrode 22 at crystalline aluminum oxide layer 20.Gate electrode 22 can be the conductive layer of work function more than or equal to about 4eV.For example, gate electrode 22 can be tantalum nitride (TaN) layer or other layer with analog material character.Can form mask M1 at gate electrode 22.Mask M1 can limit the zone that can form grid.Can carry out anisotropic etching (or similar technology) to the layer around the mask M1, until expose the part of the top surface of substrate 10, thus form gate stack structure 23.
As shown in Figure 7, can utilize ion implantation that first conductive impurity 25 is infused in the substrate 10, thereby in substrate 10, form the first shallow impurity range 12a and the second shallow impurity range 14a.Gate stack structure 23 can be used as mask in ion implantation process.In this example, first conductive impurity 25 can be different from the impurity that is infused in the substrate 10.For example, if substrate 10 comprises p type impurity, then first conductive impurity 25 can be a n type impurity.Selectively, if substrate 10 comprises n type impurity, then first conductive impurity 25 can be a p type impurity.
With reference to Fig. 8, can on each side surface of gate stack structure 23, form grid separator 24.Can form grid separator 24 by silicon oxide film or other material membrane with similar or similar substantially material character.Can utilize ion implantation that second conductive impurity 26 is infused in the substrate 10, thereby form dark impurity range in the first shallow impurity range 12a and the second shallow impurity range 14a each.
The ion implantation that is used to inject second conductive impurity 26 can utilize gate stack structure 23 and grid separator 24 as mask.The type of second conductive impurity 26 can be identical with the type of first conductive impurity 25.For example, if substrate 10 comprises p type impurity, then second conductive impurity 26 can be n type impurity.Selectively, if substrate 10 comprises n type impurity, then second conductive impurity 26 can be p type impurity.
The ion of second conductive impurity 26 injects can be greater than injecting energy by injecting first conductive impurity 25 with the ion that forms the first shallow impurity range 12a and the second shallow impurity range 14a.Therefore, second conductive impurity 26 can be injected into the degree of depth darker than first conductive impurity.For example, the first shallow impurity range 12a and dark zone or the part of the second shallow impurity range 14a that form by injecting first conductive impurity 25 of second conductive impurity 26 ratio that can arrive substrate 10.Therefore, the zone that is not covered by grid separator 24 of substrate can than the region doping that is covered by grid separator 24 get darker (for example, be doped into the darker degree of depth), obtain first impurity range 12 and second impurity range 14 of lightly doped drain (LDD) type, as shown in Figure 9.Can carry out subsequent technique according to conventional method.
Still with reference to Fig. 9, first impurity range 12 of LDD type can comprise 12d of first and second portion 12s.The 12d of first can be that surface apart from substrate 10 is with first depth d
1Inject the ion implanted region of conductive impurity ions.First depth d
1Can be apart from the dark relatively degree of depth in the surface of substrate 10.Second portion 12s can be that surface apart from substrate 10 is with second depth d
2Inject the ion implanted region of conductive impurity ions.Second depth d
2Can be apart from the shallow relatively degree of depth in the surface of substrate 10.Therefore, first depth d
1Can be greater than second depth d
2
Shown in Fig. 9 was further, second impurity range 14 of LDD type can comprise 14d of first and second portion 14s.The 14d of first can be that surface apart from substrate 10 is with first depth d
1Inject the ion implanted region of conductive impurity ions.As mentioned above, first depth d
1Can be apart from the dark relatively degree of depth in the surface of substrate 10.Second portion 14s can be that surface apart from substrate 10 is with second depth d
2Inject the ion implanted region of conductive impurity ions.As mentioned above, second depth d
2Can be apart from the shallow relatively degree of depth in the surface of substrate 10.
As mentioned above, the degree of depth of the impurity among the 12d of first of first impurity range 12 can be identical or basic identical with the degree of depth of impurity among the 14d of first of second impurity range 14.Similarly, the degree of depth of the impurity among the second portion 12s of first impurity range 12 can be identical or basic identical with the degree of depth of impurity among the second portion 14s of second impurity range 14.
Back with reference to Fig. 1, according to example embodiment, can form crystalline oxide materials layer (for example crystalline aluminum oxide layer), replace non-crystalline material layer 20a.In this example, the heat treatment of carrying out in Fig. 3 can be the crystallization processes again that alumina layer is carried out.
Hereinafter, will describe experimental example, described experimental example shows band gap about crystalline aluminum oxide (Al
2O
3) layer and increase, wherein, obtain described crystalline aluminum oxide layer according to described wet oxidation and the follow-up heat treatment method of utilizing of example embodiment.
Figure 10 be illustrate according to example embodiment to Al
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map wherein, obtains this Al by carrying out heat treatment after the execution wet oxidation under relatively high pressure and relative low temperature
2O
3Layer.
Figure 11 illustrates having the Al of the x x ray diffraction analysis x result shown in Figure 10
2O
3The result's that the reflection electron-energy-loss spectrum (REELS) that layer is carried out is analyzed image.The Al that is used for the REELS analysis of execution Figure 11
2O
3Layer had experienced the densification process that carries out under 800 ℃ temperature before carrying out wet oxidation process.
In Figure 10, the first curve G1 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (crystallization → wet oxidation → 1000 ℃ of go down hydroxyl-removal and crystallizations again).The second curve G2 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 1100 ℃ of following crystallization → wet oxidations →) in 600 ℃ of hydroxyl-removals that go down → crystallization again under 1000 ℃.
The 3rd curve G3 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 800 ℃ of following densification → wet oxidations →) 1000 ℃ of go down hydroxyl-removal and crystallizations.The 4th curve G4 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 800 ℃ of following densification → wet oxidations →) at 600 ℃ of hydroxyl-removals that go down → 1000 ℃ of following crystallizations.The 5th curve G5 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, and wherein, obtains this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (wet oxidation → 1000 ℃ of go down hydroxyl-removal and crystallizations).The 6th curve G6 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, and wherein, obtains this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (wet oxidation → at 600 ℃ of hydroxyl-removals that go down → 1000 ℃ of following crystallizations).
With reference to Figure 10, as from shown in the variation between the curve of the first curve G1 to the, six curve G6, peak P1 disappears, and wherein, peak P1 occurs when the crystalline aluminum oxide layer has γ phase crystal structure.
Therefore, when utilizing example embodiment to make the amorphous nickel/phosphorus/aluminium oxide layer be transformed into the crystalline aluminum oxide layer, in the crystalline aluminum oxide layer of gained, can suppress the γ phase.Therefore, according to example embodiment, the amorphous nickel/phosphorus/aluminium oxide layer is transformed in the technology of crystalline aluminum oxide layer, the crystal structure of alumina layer or crystalline texture can be transformed into band gap greater than κ phase or the α phase of the band gap of γ phase mutually from γ.For example, the crystal structure of the alumina layer of gained can have the band gap more than or equal to about 7.0eV.
With reference to Figure 11, be used for obtaining the x x ray diffraction analysis x result's of Figure 10 Al
2O
3The band gap of layer is about 6.87eV, and this is greater than the Al with γ phase crystal structure
2O
3The band gap (6.5eV) of layer.Yet, Al
2O
3The degree that the band gap of layer increases can be owing to densification process reduces.
Figure 12 be illustrate according to example embodiment to Al
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map wherein, obtains this Al by carrying out at least one times heat treatment after the execution wet oxidation process under atmospheric pressure and relative high temperature
2O
3Layer.
Figure 13 illustrates having the Al of the x x ray diffraction analysis x result shown in Figure 12
2O
3The result's that the REELS that layer is carried out analyzes image, wherein, the result who is analyzed by this REELS obtains Al
2O
3Band gap.
In Figure 12, the first curve G11 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 1000 ℃ of following wet oxidations →) 1000 ℃ of go down hydroxyl-removal and crystallizations again.The second curve G22 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 1000 ℃ of following wet oxidations →) in 600 ℃ of hydroxyl-removals that go down → crystallization again under 1000 ℃.
The 3rd curve G33 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (in 1100 ℃ of following crystallizations →) at 700 ℃ of following wet oxidations → 1000 ℃ of go down hydroxyl-removal and crystallizations again.The 4th curve G44 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (in 1100 ℃ of following crystallizations →) at 700 ℃ of following wet oxidations → in 600 ℃ of hydroxyl-removals that go down → crystallization again under 1000 ℃.
The 5th curve G55 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, and wherein, obtains this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 700 ℃ of following wet oxidations → 1000 ℃ of go down hydroxyl-removal and crystallizations).The 6th curve G66 shows the result of the x x ray diffraction analysis x that the crystalline aluminum oxide layer is carried out, wherein, obtain this crystalline aluminum oxide layer by the amorphous nickel/phosphorus/aluminium oxide layer being carried out a plurality of technologies (at 700 ℃ of following wet oxidations →) at 600 ℃ of hydroxyl-removals that go down → 1000 ℃ of following crystallizations.
With reference to Figure 12, as from shown in the variation of the first curve G11 to the, six curve G66, peak P2 can reduce, and wherein, peak P2 occurs when alumina layer has γ phase crystal structure.Therefore, about as described in Figure 10, can suppress the formation of the γ phase crystal structure in the alumina layer as above.
With reference to Figure 13, the band gap of alumina layer increases to about 7.42eV, and this is corresponding at the Al with κ phase crystal structure
2O
3In the band gap observed.Can further increase this band gap by changing (such as improving) process conditions (such as the temperature of wet oxidation, remove the temperature etc. of temperature, crystallization or the optimization of H or OH).According at least some example embodiment, can make Al by changing and/or improving process conditions
2O
3The crystal transition of layer becomes the α phase.
Therefore, according to example embodiment, can form crystalline aluminum oxide layer 20 so that crystalline aluminum oxide layer 20 have band gap can be greater than the about α phase crystal structure of 8eV.
Figure 14 be illustrate according to example embodiment to crystalline A l
2O
3The result's of the x x ray diffraction analysis x that layer is carried out curve map, wherein, by to amorphous Al
2O
3Layer is only carried out the heat treatment under 1100 ℃ and is not carried out wet oxidation and obtain this crystalline A l
2O
3Layer.Figure 15 is the Al that illustrates the x x ray diffraction analysis x result with Figure 14
2O
3The result's that the REELS that layer is carried out analyzes image.
With reference to Figure 14, do not carry out the crystalline A l that wet oxidation obtains by only carrying out the heat treatment under 1100 ℃
2O
3Layer has γ phase crystal structure.With reference to Figure 15, this Al
2O
3The band gap of layer is about 6.56eV.
Figure 10 to Figure 13 and Figure 14 and Figure 15 are compared, when the electric charge that forms crystallization according to example embodiment stops Al
2O
3During layer, crystalline A l
2O
3The band gap of layer can be greater than the crystalline A l with γ phase crystal structure
2O
3The band gap of layer.
With reference to Figure 16 to Figure 22 method according to the manufacturing charge trap memory device of example embodiment is described.For the purpose of concise and to the point, with the explanation of omitting to said elements.
With reference to Figure 16, can in substrate 10, sequentially pile up tunneling membrane 16, electric charge capture layer 18 and amorphous nickel/phosphorus/aluminium oxide layer 20a.Can form metal level 40 at amorphous nickel/phosphorus/aluminium oxide layer 20a.Amorphous nickel/phosphorus/aluminium oxide layer 20a can be used as electric charge barrier layer.The space lattice of metal level 40 can with alpha-aluminium oxide (crystalline A l
2O
3Layer) the similar or basic simlarity of space lattice.For example, metal level 40 can be titanium carbonitride (TiCN) layer, rhodium oxide (Rh
2O
3) layer, crystal orientation be ruthenium (Ru) layer of (0001) or similarly layer.
After forming metal level 40, can carry out heat treatment to the resulting structures that comprises metal level 40.Can under temperature given or expectation, (for example, in the temperature range between about 1000 ℃ and about 1300 ℃, comprise about 1000 ℃ and about 1300 ℃) and carry out described heat treatment.Can utilize rapid thermal annealing (RTA) or the similarly such heat treatment of method execution.
After this heat treatment, amorphous nickel/phosphorus/aluminium oxide layer 20a becomes crystalline aluminum oxide layer 20c, as shown in figure 17.In this heat treatment process, the crystalline state of metal level 40 can affect amorphous nickel/phosphorus/aluminium oxide layer 20a, and amorphous nickel/phosphorus/aluminium oxide layer 20a can crystallization, thereby has the space lattice of or basic simlarity similar to the space lattice of metal level 40.Because the space lattice of metal level 40 is similar to the space lattice of alpha-aluminium oxide, so the crystalline phase of the crystalline aluminum oxide layer 20c of the Figure 17 that forms by this heat treatment can become the α phase.
With reference to Figure 18, can form mask M2 at crystalline aluminum oxide layer 20c.This mask can limit gate regions.Etching sequentially is formed on metal level 40, crystalline aluminum oxide layer 20c, electric charge capture layer 18 and the tunneling membrane 16 around the mask M2.Can carry out this etch process, till exposing substrate 10.Figure 19 shows the resulting structures after carrying out this etch process.Then, can remove mask M2.Can form gate stack 50 in substrate 10 by this etch process.
With reference to Figure 20, can in substrate 10, form the first shallow impurity range 12a and the second shallow impurity range 14a.As shown in figure 21, can form the grid separator 24 that cover gate is piled up 50 side surface, and can form first impurity range 12 and second impurity range 14 by conductive impurity 26 being injected among the first shallow impurity range 12a and the second shallow impurity range 14a.One in first impurity range 12 and second impurity range 14 can be used as source area, and another can be used as the drain region.
Figure 22 shows the example embodiment of the charge trap memory device that forms by above technology.
Technology shown in Figure 20 to Figure 22 can be identical with the technology shown in Fig. 7 to Fig. 9.
In the example embodiment of the method for making charge trap memory device, can be omitted in and form the independent technology that α phase crystalline aluminum oxide layer 20c will be used to form the material layer removal of α phase crystalline aluminum oxide layer 20c afterwards.Therefore, can simplified manufacturing technique with respect to conventional art.
In the manufacture method according to example embodiment, when metal level 40 is Rh
2O
3When layer, metal level 40 can be transformed into the insulation phase from conductive phase mutually, vice versa.Because metal level 40 is as gate electrode, thus the metal level 40 in the structure that finally obtains can be conductive phase mutually.
Therefore, for example, when metal level 40 is Rh
2O
3When layer, the metal level 40 that is in the insulation phase being carried out the heat treatment (hereinafter, being called first heat treatment) described with reference to Figure 16 afterwards, can carry out second heat treatment to metal level 40, thereby make metal level 40 be transformed into mutually conductive phase.Carry out second heat treatment in the temperature range that can under normal pressure and between about 1000 ℃ and about 1300 ℃, (comprise about 1000 ℃ and about 1300 ℃).Can utilize rapid thermal annealing (RTA) or similar approach to carry out second heat treatment.
Can utilize mask M2 to carry out first heat treatment after finishing etch process.For example, after the resulting structures that obtains Figure 19, can carry out first heat treatment.In this example, can under the state that has mask M2, carry out first heat treatment, perhaps can after removing mask M2, carry out first heat treatment.
Although described example embodiment about H or OH are injected in the amorphous nickel/phosphorus/aluminium oxide layer here, it should be understood that and H and/or OH can be injected in the amorphous nickel/phosphorus/aluminium oxide layer.In addition, example embodiment should not be confined to the alumina material layer.On the contrary, can implement and/or utilize example embodiment in conjunction with the metal oxide layer with similar quality and/or purposes.
Although specifically illustrate and described the present invention with reference to example embodiment of the present invention, but those of ordinary skills should be understood that, in the situation that does not break away from the spirit and scope of the present invention that limit such as claim, wherein can make in form and the various changes on the details.
Claims (27)
1. method that increases the band gap of alumina layer may further comprise the steps:
Forming the amorphous nickel/phosphorus/aluminium oxide layer on the film down;
H or OH are incorporated in the amorphous nickel/phosphorus/aluminium oxide layer;
Make the amorphous nickel/phosphorus/aluminium oxide layer crystallization that comprises H or OH.
2. the method for claim 1, wherein use a kind of method in wet oxidation, ion implantation and the plasma doping method that H or OH are introduced in the amorphous nickel/phosphorus/aluminium oxide layer.
3. method as claimed in claim 2 wherein, is carried out wet oxidation under the atmospheric pressure and first temperature, perhaps carry out wet oxidation being higher than atmospheric pressure and being lower than under second temperature of first temperature.
4. the step of amorphous nickel/phosphorus/aluminium oxide layer crystallization is comprised:
The amorphous nickel/phosphorus/aluminium oxide layer is carried out first heat treatment, wherein, in 800 ℃ to 1300 ℃ temperature range, be included under 800 ℃ and 1300 ℃, carry out first heat treatment.
5. method as claimed in claim 4 also comprises:
The amorphous nickel/phosphorus/aluminium oxide layer is carried out second heat treatment, wherein, under the temperature of the crystallization temperature that is lower than the amorphous nickel/phosphorus/aluminium oxide layer, carry out second heat treatment.
6. the method for claim 1, wherein in single technical process, carry out at lower film forming the step of amorphous nickel/phosphorus/aluminium oxide layer and H or OH are incorporated into step in the amorphous nickel/phosphorus/aluminium oxide layer.
7. the method for claim 1, wherein when introducing H or OH, make the crystallization of amorphous nickel/phosphorus/aluminium oxide layer.
8. method as claimed in claim 7 wherein, utilizes vapour deposition process or atomic layer deposition method to form the amorphous nickel/phosphorus/aluminium oxide layer.
9. the method for claim 1, wherein the alumina layer of crystallization comprises the crystalline phase of band gap greater than 7.0eV.
10. method of making charge trap memory device said method comprising the steps of:
Method according to claim 1 forms the crystalline aluminum oxide layer,
Wherein, described film down is an electric charge capture layer.
11. method as claimed in claim 10, wherein, the alumina layer of crystallization comprises the crystalline phase of band gap greater than 7.0eV.
12. method as claimed in claim 10 wherein, uses a kind of method in wet oxidation, ion implantation and the plasma doping method that H or OH are introduced in the amorphous nickel/phosphorus/aluminium oxide layer.
13. method as claimed in claim 12 wherein, is carried out wet oxidation under the atmospheric pressure and first temperature, perhaps carry out wet oxidation being higher than atmospheric pressure and being lower than under second temperature of first temperature.
14. method as claimed in claim 10 wherein, comprises the step of amorphous nickel/phosphorus/aluminium oxide layer crystallization:
The amorphous nickel/phosphorus/aluminium oxide layer is carried out first heat treatment, wherein, in 800 ℃ to 1300 ℃ temperature range, be included under 800 ℃ and 1300 ℃, carry out first heat treatment.
15. method as claimed in claim 14 also comprises:
The amorphous nickel/phosphorus/aluminium oxide layer is carried out second heat treatment, wherein, under the temperature of the crystallization temperature that is lower than the amorphous nickel/phosphorus/aluminium oxide layer, carry out second heat treatment.
16. method as claimed in claim 10, wherein, after introducing H or OH, described method also comprises:
Before making the crystallization of amorphous nickel/phosphorus/aluminium oxide layer, make the amorphous nickel/phosphorus/aluminium oxide layer densification that comprises H or OH.
17. method as claimed in claim 10 wherein, also comprises the step in H or the OH introducing amorphous nickel/phosphorus/aluminium oxide layer:
When introducing H or OH, in oxygen atmosphere, the amorphous nickel/phosphorus/aluminium oxide layer is carried out first heat treatment.
18. method as claimed in claim 10, wherein, under the oxygen enrichment state after electric charge capture layer forms the amorphous nickel/phosphorus/aluminium oxide layer, introduce H.
19. method as claimed in claim 18 also comprises:
Make the amorphous nickel/phosphorus/aluminium oxide layer densification that comprises H.
20. method as claimed in claim 10, wherein, electric charge capture layer is a silicon nitride layer.
21. method of making charge trap memory device, described charge trap memory device comprises by sequentially being stacked on the gate stack that suprabasil tunneling membrane, electric charge capture layer, α phase crystalline aluminum oxide layer and gate electrode form, said method comprising the steps of:
On electric charge capture layer, form the amorphous nickel/phosphorus/aluminium oxide layer;
Form metal level at the amorphous nickel/phosphorus/aluminium oxide layer, the space lattice of metal level is similar to the space lattice of α phase crystalline aluminum oxide layer;
By the gains that comprise metal level are carried out heat treatment, make the amorphous nickel/phosphorus/aluminium oxide layer be transformed into α phase crystalline aluminum oxide layer.
22. method as claimed in claim 21, wherein, the step that makes the amorphous nickel/phosphorus/aluminium oxide layer be transformed into α phase crystalline aluminum oxide layer also comprises:
Form mask at metal level, described mask limits the zone that will form gate stack;
Etching sequentially is formed on metal level, amorphous nickel/phosphorus/aluminium oxide layer, electric charge capture layer and the tunneling membrane around the described mask;
The gains that comprise metal level are carried out heat treatment.
23. method as claimed in claim 21 wherein, makes after the amorphous nickel/phosphorus/aluminium oxide layer is transformed into α phase crystalline aluminum oxide layer, described method also comprises:
Form mask at metal level, described mask limits the zone that will form gate stack;
Etching sequentially is formed on metal level, α phase crystalline aluminum oxide layer, electric charge capture layer and the tunneling membrane around the described mask;
Remove described mask.
24. method as claimed in claim 23 wherein, after removing mask, is carried out heat treatment to the gains that comprise metal level.
25. method as claimed in claim 21, wherein, by TiCN layer, Rh
2O
3Layer, crystal orientation are a kind of formation metal level in the Ru layer of (0001).
26. method as claimed in claim 25 also comprises:
When metal level is Rh
2O
3During layer, carry out for making metal level be transformed into the heat treatment of conductive layer.
27. method as claimed in claim 21 wherein, under normal pressure and in the temperature range between 1000 ℃ and 1300 ℃, is included under 1000 ℃ and 1300 ℃, carries out described heat treatment.
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| KR100481848B1 (en) * | 1998-12-15 | 2006-05-16 | 삼성전자주식회사 | Manufacturing method of dielectric film without chemical defect |
| US6858865B2 (en) | 2001-02-23 | 2005-02-22 | Micron Technology, Inc. | Doped aluminum oxide dielectrics |
| KR20050056408A (en) * | 2003-12-10 | 2005-06-16 | 주식회사 하이닉스반도체 | Method of manufacturing capacitor for semiconductor device |
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