CN102231365B - Preparation method of non-volatile charge storage device, non-volatile charge storage device and application of device - Google Patents
Preparation method of non-volatile charge storage device, non-volatile charge storage device and application of device Download PDFInfo
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- 238000003860 storage Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 21
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 27
- 230000008021 deposition Effects 0.000 claims description 27
- 238000009825 accumulation Methods 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000006557 surface reaction Methods 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 230000005641 tunneling Effects 0.000 abstract description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 6
- 229910052593 corundum Inorganic materials 0.000 abstract 6
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 6
- 230000001376 precipitating effect Effects 0.000 abstract 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000004506 ultrasonic cleaning Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003949 trap density measurement Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a non-volatile charge storage device, the non-volatile charge storage device and application thereof. The preparation method of the non-volatile charge storage device comprises the following specific steps: a) precipitating Al2O3 on the surface of a substrate by use of an atomic layer chemical vapor deposition method so as to form a tunneling layer; b) precipitating a layer of (HfO2)x(Al2O3)1-x film serving as a storage layer on the surface of the tunneling layer by use of the atomic layer chemical vapor deposition method; and c) precipitating a layer of Al2O3 serving as a barrier layer on the surface of the (HfO2)x(Al2O3)1-x storage layer by use of the chemical vapor deposition method. The non-volatile charge storage device comprises the tunneling layer, the storage layer and the barrier layer which are successively connected; Al2O3 is used as the tunneling layer and barrier layer of the storage device, and (HfO2)x(Al2O3)1-x is used as the storage layer of the device. By using the method, the writing-in and erasing speeds of the device can be well improved, and simultaneously, the preparation method is simple to operate and easy to control.
Description
Technical field
The present invention relates to a kind of non-volatile charge storage device, its preparation method and application, belong to the microelectronic material field.
Background technology
In decades, the Moore's Law of one of founder's of Intel Company Gordon doctor E.Moore prophesy in 1964 has been followed in the development of integrated circuit substantially: integrated parts number on the one single chip of integrated circuit, it is the integrated level of integrated circuit, doubled feature size downsizing in per 12 to 18 months
Doubly.Along with the characteristic size of device is more and more less, the non-volatile semiconductor storage unit of traditional floating gate type faces serious electric leakage problem.Constantly the reducing of tunnel layer size in the floating gate type memory spare is to such an extent as to the electric charge total loss that defective will cause storing in the multi-crystal silicon floating bar.In order to solve this difficult problem, polycrystalline silicon-oxide-nitride--oxide-silicon (SONOS) type semiconductor storage unit is extensively studied.But, studies show that and utilize nitride (Si
3N
4) as relatively poor, the simultaneously traditional SiO of data retention of the charge storage device of accumulation layer preparation
2The thickness on tunnel layer and barrier layer also is more and more thinner, because the tunnelling current that quantum tunneling effect causes increases sharply, the result causes SiO
2Layer can not play the effect of dielectric, and the leakage current of device has reached unaffordable stage.Adopt high-k (high-k) material guaranteeing that raceway groove is had under the condition of identical control ability, the physical thickness of gate dielectric layer increases, so the Direct Tunneling between grid layer and raceway groove will reduce greatly.
High-k (high-k) (HfO
2)
x(Al
2O
3)
1-xBinary oxide studied proof can well reduce leakage current.Than pure HfO
2, (HfO
2)
x(Al
2O
3)
1-xBinary oxide has high charge trap density, can significantly improve the charge storage performance.Compare SiO
2, Al
2O
3Have high dielectric constant (9) and wide energy gap (8.8eV), so adopt Al
2O
3Replace SiO as tunnel layer and barrier layer
2, can well reduce leakage current and the memory property that improves device.
Atomic layer chemical vapor deposition (ALD) is that the high-k field of material preparation just has challenging a kind of technology of preparing developing.Its principle is to utilize gaseous sources in successively (layer by layer) growth of self-saturation realization of substrate surface absorption or reaction, the thickness of film former does not rely on the growth parameter(s)s such as underlayer temperature, vapour pressure, source flux in operation window, only relevant with the number of cycle period.Because its unique self-limiting growth process, ald film forming have accurate THICKNESS CONTROL, excellent three-dimensional stickiness becomes the advantages such as film uniformity with large tracts of land, unique advantage aspect preparation ultrathin film, nanostructure.
Summary of the invention
The invention provides a kind of preparation method of non-volatile charge storage device, simple to operate, be easy to control, gained nonvolatile memory spare can improve writing and erasing speed of device well, significantly improves the charge storage performance of device.
The present invention also provides above-mentioned preparation method's gained non-volatile charge storage device.
The present invention also provides the application of above-mentioned non-volatile charge storage device in information storage and non-volatile semiconductor storage unit.
The preparation method of described non-volatile charge storage device, concrete steps are as follows:
A) with Al (CH
3)
3As source metal, water generates Al with the atomic layer chemical vapor deposition method at substrate surface and oxygen source reaction as oxygen source
2O
3, form tunnel layer;
B) with HfCl
4As source metal, water generates HfO with the atomic layer chemical vapor deposition method at substrate surface and oxygen source reaction as oxygen source
2, then with Al (CH
3)
3As source metal, water generates Al with the atomic layer chemical vapor deposition method at substrate surface and oxygen source reaction as oxygen source
2O
3, iterative cycles like this is at tunnel layer surface deposition one deck (HfO
2)
x(Al
2O
3)
1-xFilm is as accumulation layer, wherein 0.9 〉=x 〉=0.5.Preferred x=0.8, by the regulation and control number of deposition cycles, control x value;
C) with Al (CH
3)
3As source metal, water uses the atomic layer chemical vapor deposition method at (HfO as oxygen source
2)
x(Al
2O
3)
1-xAccumulation layer surface deposition one deck Al
2O
3As the barrier layer.
As preferably, the thickness of tunnel layer is 2-4nm, and the thickness on barrier layer is 8-10nm.
Preferably deposition platinum is as top electrode on the barrier layer, and substrate is Si.
The concrete steps of the described atomic layer chemical vapor deposition method of atomic layer chemical vapor deposition metal oxide method are: source metal follows nitrogen to enter the settling chamber, with substrate surface reactions and reach capacity, oxygen source is brought cavity into by nitrogen and source metal generation surface reaction generates metal oxide afterwards.The schematic diagram of a cyclic process as shown in Figure 1.From Fig. 1 (a), find out that nitrogen carries source metal and enters deposition chamber; The silicon substrate reaction of source metal and hydroxyl (OH) terminal, and make it to reach capacity (shown in Fig. 1 (b)); Subsequently, the water as oxygen source enters cavity, generation surface reaction (Fig. 1 (c)), thereby the metal oxide (Fig. 1 (d)) of acquisition expection.
Described non-volatile charge storage device comprises tunnel layer, accumulation layer and the barrier layer that is linked in sequence, and utilizes Al
2O
3As tunnel layer and the barrier layer of memory device, (HfO
2)
x(Al
2O
3)
1-xBinary oxide is as the accumulation layer of device.
As preferably, for sinking to the bottom, Pt is top electrode with Si, and the structure of described non-volatile charge storage device is Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3/ Pt.
The application of described non-volatile charge storage device in information storage and non-volatile semiconductor storage unit.Use Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3Method and the principle of/Pt charge storage device are as follows:
A) Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3The taproot structure of/Pt charge storage device is Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3Sandwich structure (as shown in Figure 2).
B) and Si substrate relative when the Pt electrode applies a positive voltage, and electric field points to substrate by electrode.Along with executing alive increase, electric field strength constantly increases.The p-Si substrate surface reaches transoid, form the surface electronic passage, and tunnelling is crossed Al under electric field action
2O
3Tunnel layer enters into Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3Accumulation layer is caught by the electron trap attitude, reaches the effect of storage, and this process is exactly Si/Al
2O
3/ Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3/ Al
2O
3The ablation process of/Pt memory device.
C) when cutting off the electricity supply, electronics is stored in (HfO
2)
x(Al
2O
3)
1-xIn the accumulation layer, and can not leak, thereby play the effect of charge storage.
D) and Si substrate relative when the Pt electrode applies a negative voltage, and electric field points to electrode by substrate.On the one hand, the hole in the p-Si substrate is issued to (HfO at electric field action
2)
x(Al
2O
3)
1-xAccumulation layer and store electrons are compound; On the other hand, be stored in (HfO
2)
x(Al
2O
3)
1-xIn electronics under the effect of electric field force, pass tunnel layer and come back to substrate.Two kinds of machine-processed actings in conjunction reach Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3The erase operation of/Pt memory device.
Above-mentioned atomic layer chemical vapor deposition method prepares Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3Charge storage structure can be good at improving writing and erasing speed of device, simultaneously this preparation method so that tunnel layer, accumulation layer and barrier layer in a settling chamber, can complete, simple to operate, be easy to control.Use the Si/Al of the method preparation
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3/ Pt memory device has following beneficial effect:
A) regulate the atomic layer deposition cycles number of times, deposition (HfO
2)
0.8(Al
2O
3)
0.2As accumulation layer, the result shows that this structure can access large charge storage hysteresis window.Fig. 3 show when scanning voltage be ± during 2V, almost do not have the window appearance, show the charge storage phenomenon does not occur at this moment.When scanning voltage be ± during 5V, had obvious hysteresis window.When scanning voltage be ± during 14V, memory window is 5.7V.
B) Fig. 4 shows, than pure hafnium oxide (HfO
2) as accumulation layer, (HfO
2)
0.8(Al
2O
3)
0.2The binary oxide film can improve the charge storage performance of device significantly.This is because Al
2O
3With HfO
2Form binary oxide, can improve the trap states density in the film, thereby write under the voltage (HfO identical
2)
0.8(Al
2O
3)
0.2Has higher magnitude of the stored charge.
C) as seen from Figure 5, along with tunnel layer Al
2O
3Constantly reducing of thickness, Si/Al
2O
3/ (HfO
2)
0.8(Al
2O
3)
0.2/ Al
2O
3Writing with erasing speed of/Pt memory device constantly increases.For adopting 2nmAl
2O
3As tunnel layer, when memory window was 1V, corresponding writing with erasing speed was respectively 10V, 0.1ms and-10V, 1ms.
D) Fig. 6 is: 900 ℃, and after annealing 30 seconds in the nitrogen atmosphere, Si/Al
2O
3/ (HfO
2)
0.8(Al
2O
3)
0.2/ Al
2O
3The high-resolution transmission electron microscopy figure of structure.Al as we can see from the figure
2O
3/ (HfO
2)
0.8(Al
2O
3)
0.2/ Al
2O
3Three-decker, and at (HfO
2)
0.8(Al
2O
3)
0.2In do not find crystal region, and then Al can be described
2O
3Adding can improve the crystallization temperature of accumulation layer, avoided the formation of electric leakage path after the crystallization, thereby improved the charge storage performance of device.Because the impact of high annealing has formed atom diffusion zone between layers, can be found out by the contrast of three-layer thin-film, the tunnel layer of 2nm and the accumulation layer of 7nm, and have the diffusion phenomena of atom to occur between the barrier layer of accumulation layer and 9nm.
Description of drawings
Fig. 1: cyclic process schematic diagram of atomic layer chemical vapor deposition metal oxide, (a) source metal enters cavity (M represents metal, L
1And L
2Represent respectively halogen, CH
3With functional groups such as alkyl, in this example, when M=Al, L
1=L
2=CH
3Work as M=Hf, L
1=L
2=Cl); (b) source metal and surface reaction reach capacity; (c) oxygen source enters cavity; (d) obtain metal oxide.
Fig. 2: Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3The structural representation of/Pt charge storage device.Wherein, be close to the Al that Si sinks to the bottom
2O
3As tunnel layer, the Al of next-door neighbour Pt electrode
2O
3As the barrier layer, (HfO
2)
x(Al
2O
3)
1-xAs accumulation layer.
Fig. 3: under the high frequency situations (1MHz), capacitance-voltage characteristics (M=Pt, A=Al under the different gated sweep voltages of M-A-HA-A-S charge storage device
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate).Wherein the x axle represents to be applied to the voltage (unit is volt) on the Pt electrode, and the y axle represents normalized storage capacitance.
Fig. 4: M-A-HA-A-S (M=Pt, A=Al
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate) and M-A-H-A-S (M=Pt, A=Al
2O
3, H=HfO
2, the S=silicon substrate) and flat band voltage under the different gated sweep voltages of charge storage device changes.Wherein the x axle represents to be applied to the scanning voltage (unit is volt) on the Pt electrode, and the y axle represents with respect to the variation of flat band voltage under the quasi-static situation (unit is volt).
Fig. 5: M-A-HA-A-S (M=Pt, A=Al with different tunnel layer thickness
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate) and write and clash characteristic during the charge storage.X axle time of representing to write and clash (unit for second) wherein, the y axle represents relatively to write, the time of clashing is that 0 o'clock flat band voltage changes (unit is volt).
Fig. 6: after annealing 30 seconds in 900 ℃ of nitrogen atmospheres, Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3The high-resolution transmission electron microscopy figure of structure.
Embodiment
Embodiment 1: based on p-Si substrate, Si/Al
2O
3/ (HfO
2)
0.8(Al
2O
3)
0.2/ Al
2O
3The preparation process of/Pt charge storage device is specific as follows:
(a) the p-Si substrate is put into proper amount of acetone with substrate, after the ultrasonic cleaning, use the deionized water ultrasonic cleaning, rinse the residual impurity of substrate surface.Then substrate is put into hydrofluoric acid and is soaked, and removes oxide on surface, re-uses the deionized water ultrasonic cleaning, puts into the atomic layer chemical vapor deposition cavity after drying up with high pure nitrogen in order to deposit film.
(b) adopt HfCl in the deposition process
4And Al (CH
3)
3As source metal, water is oxygen source.Al (CH
3)
3Follow nitrogen to enter cavity, with the reaction of the surface of silicon of hydroxy terminal and reach capacity, oxygen source is brought cavity and source metal generation surface reaction generation Al into by nitrogen afterwards
2O
3, form tunnel layer, by control atomic layer deposition cycles coefficient, deposit thickness is the Al of 2nm
2O
3As tunnel layer.
(c) when the end of tunnel layer deposition, at Al
2O
3Tunnel layer surface deposition (HfO
2)
0.8(Al
2O
3)
0.2Accumulation layer.Atomic ratio and film thickness by regulation and control number of deposition cycles control Hf and Al.Starting stage, HfCl
4Source metal is deposited on Al
2O
3The surface reaches capacity the surface, the oxygen source and the HfCl that are written into by air-flow subsequently
4Contact, and surface reaction occurs, generate one deck HfO
2Then, Al (CH
3)
3Follow gas to enter cavity, be deposited on HfO
2Surface, the oxygen source that enters afterwards with it cavity react and generate Al
2O
3Like this iterative cycles, just at the tunnel layer surface deposition the thick (HfO of one deck 7nm
2)
0.8(Al
2O
3)
0.2Film.The thickness of accumulation layer generally can be 6-8nm.
(d) (HfO
2)
0.8(Al
2O
3)
0.2The accumulation layer deposition finishes, at the thick Al of its surface deposition one deck 9nm
2O
3Dielectric layer, as the barrier layer, forming process such as step (b).
(e) after above-mentioned preparation process finishes, device is placed quick anneal oven, at 900 ℃, annealing is 30 seconds in the nitrogen atmosphere.
(f) platinum (Pt) is as top electrode, and the method by magnetron sputtering is deposited on above the device of annealed processing.Sink to the bottom the side at Si and apply the last layer conductive silver glue as bottom electrode.
Under the high frequency situations (1MHz), capacitance-voltage characteristics (M=Pt, A=Al under the different gated sweep voltages of M-A-HA-A-S charge storage device
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate) as shown in Figure 3.
Comparative examples 1: based on p-Si substrate, Si/Al
2O
3/ HfO
2/ Al
2O
3The preparation process of/Pt charge storage device is specific as follows:
(a) the p-Si substrate is put into proper amount of acetone with substrate, after the ultrasonic cleaning, use the deionized water ultrasonic cleaning, rinse the residual impurity of substrate surface.Then substrate is put into hydrofluoric acid and is soaked, and removes oxide on surface, re-uses the deionized water ultrasonic cleaning, puts into the atomic layer chemical vapor deposition cavity after drying up with high pure nitrogen in order to deposit film.
(b) adopt HfCl in the deposition process
4And Al (CH
3)
3As source metal, water is oxygen source.Al (CH
3)
3Follow nitrogen to enter cavity, with the reaction of the surface of silicon of hydroxy terminal and reach capacity, oxygen source is brought cavity and source metal generation surface reaction generation Al into by nitrogen afterwards
2O
3, form tunnel layer, by control atomic layer deposition cycles coefficient, deposit thickness is the Al of 2nm
2O
3As tunnel layer.
(c) when the end of tunnel layer deposition, at Al
2O
3Tunnel layer surface deposition HfO
2Accumulation layer.By regulation and control number of deposition cycles control film thickness.HfCl
4Source metal is deposited on Al
2O
3The surface reaches capacity the surface, the oxygen source and the HfCl that are written into by air-flow subsequently
4Contact, and surface reaction occurs, generate the thick HfO of one deck 7nm
2Film.
(d) HfO
2The accumulation layer deposition finishes, at the thick Al of its surface deposition one deck 9nm
2O
3Dielectric layer, as the barrier layer, forming process such as step (b).
(e) after above-mentioned preparation process finishes, device is placed quick anneal oven, at 900 ℃, annealing is 30 seconds in the nitrogen atmosphere.
(f) platinum (Pt) is as top electrode, and the method by magnetron sputtering is deposited on above the device of annealed processing.Sink to the bottom the side at Si and apply the last layer conductive silver glue as bottom electrode.
Embodiment 1 gained M-A-HA-A-S (M=Pt, A=Al
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate) and comparative examples 1 gained M-A-H-A-S (M=Pt, A=Al
2O
3, H=HfO
2, the S=silicon substrate) and the flat band voltage variation of charge storage device under different gated sweep voltages is as shown in Figure 4.
Embodiment 2: based on the p-Si substrate, have the Si/Al of different tunnel layer thickness
2O
3/ (HfO
2)
0.8(Al
2O
3)
0.2/ Al
2O
3The preparation process of/Pt charge storage device is specific as follows:
(a) the p-Si substrate is put into proper amount of acetone with substrate, after the ultrasonic cleaning, use the deionized water ultrasonic cleaning, rinse the residual impurity of substrate surface.Then substrate is put into hydrofluoric acid and is soaked, and removes oxide on surface, re-uses the deionized water ultrasonic cleaning, puts into the atomic layer chemical vapor deposition cavity after drying up with high pure nitrogen in order to deposit film.
(b) adopt HfCl in the deposition process
4And Al (CH
3)
3As source metal, water is oxygen source.Al (CH
3)
3Follow nitrogen to enter cavity, with the reaction of the surface of silicon of hydroxy terminal and reach capacity, oxygen source is brought cavity and source metal generation surface reaction generation Al into by nitrogen afterwards
2O
3, form tunnel layer, by control atomic layer deposition cycles coefficient, deposit thickness is 2nm respectively, the Al of 3nm and 4nm
2O
3As tunnel layer.
(c) when the end of tunnel layer deposition, at Al
2O
3Tunnel layer surface deposition (HfO
2)
0.8(Al
2O
3)
0.2Accumulation layer.Atomic ratio and film thickness by regulation and control number of deposition cycles control Hf and Al.Starting stage, HfCl
4Source metal is deposited on Al
2O
3The surface reaches capacity the surface, the oxygen source and the HfCl that are written into by air-flow subsequently
4Contact, and surface reaction occurs, generate one deck HfO
2Then, Al (CH
3)
3Follow gas to enter cavity, be deposited on HfO
2Surface, the oxygen source that enters afterwards with it cavity react and generate Al
2O
3Like this iterative cycles, just at the tunnel layer surface deposition the thick (HfO of one deck 7nm
2)
0.8(Al
2O
3)
0.2Film.
(d) (HfO
2)
0.8(Al
2O
3)
0.2The accumulation layer deposition finishes, at the thick Al of its surface deposition one deck 9nm
2O
3Dielectric layer, as the barrier layer, forming process such as step (b).
(e) after above-mentioned preparation process finishes, device is placed quick anneal oven, at 900 ℃, annealing is 30 seconds in the nitrogen atmosphere.
(f) platinum (Pt) is as top electrode, and the method by magnetron sputtering is deposited on above the device of annealed processing.Sink to the bottom the side at Si and apply the last layer conductive silver glue as bottom electrode.
Gained has M-A-HA-A-S (M=Pt, the A=Al of different tunnel layer thickness
2O
3, HA=(HfO
2)
0.8(Al
2O
3)
0.2, the S=silicon substrate) and write and clash characteristic as shown in Figure 5 during the charge storage.
Claims (8)
1. the preparation method of a non-volatile charge storage device is characterized in that concrete steps are as follows:
A) with Al (CH
3)
3As source metal, water generates Al with the atomic layer chemical vapor deposition method in substrate surface reactions as oxygen source
2O
3, form tunnel layer;
B) with HfCl
4As source metal, water generates HfO with the atomic layer chemical vapor deposition method in substrate surface reactions as oxygen source
2, then with Al (CH
3)
3As source metal, water generates Al with the atomic layer chemical vapor deposition method in substrate surface reactions as oxygen source
2O
3, iterative cycles like this is at tunnel layer surface deposition one deck (HfO
2)
x(Al
2O
3)
1-xFilm is as accumulation layer, and wherein x=0.8 by the regulation and control number of deposition cycles, controls the x value;
C) with Al (CH
3)
3As source metal, water uses the atomic layer chemical vapor deposition method at (HfO as oxygen source
2)
x(Al
2O
3)
1-xAccumulation layer surface deposition one deck Al
2O
3As the barrier layer.
2. the preparation method of non-volatile charge storage device as claimed in claim 1, the concrete steps that it is characterized in that described atomic layer chemical vapor deposition method are: source metal follows nitrogen to enter the settling chamber, with substrate surface reactions and reach capacity, oxygen source is brought cavity into by nitrogen and source metal generation surface reaction generates metal oxide afterwards.
3. the preparation method of non-volatile charge storage device as claimed in claim 1 or 2 is characterized in that deposition platinum is as top electrode on the barrier layer, and substrate is Si.
4. non-volatile charge storage device as claimed in claim 1 or 2, the thickness that it is characterized in that tunnel layer is 2-4nm, the thickness on barrier layer is 9nm.
5. non-volatile charge storage device as claimed in claim 1 or 2 is characterized in that x=0.8.
6. the non-volatile charge storage device of each preparation method's gained among the claim 1-5 is characterized in that comprising the tunnel layer, accumulation layer and the barrier layer that are linked in sequence, utilizes Al
2O
3As tunnel layer and the barrier layer of memory device, (HfO
2)
x(Al
2O
3)
1-xBinary oxide is as the accumulation layer of device.
7. non-volatile charge storage device as claimed in claim 6 is characterized in that with Si for sinking to the bottom, Pt is top electrode, and the structure of described non-volatile charge storage device is Si/Al
2O
3/ (HfO
2)
x(Al
2O
3)
1-x/ Al
2O
3/ Pt.
8. claim 6 or the 7 described non-volatile charge storage devices application in information storage and non-volatile semiconductor storage unit.
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