CN101908477B - Method for preparing gate stack of metallic nano crystal memory - Google Patents
Method for preparing gate stack of metallic nano crystal memory Download PDFInfo
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- CN101908477B CN101908477B CN2010102425845A CN201010242584A CN101908477B CN 101908477 B CN101908477 B CN 101908477B CN 2010102425845 A CN2010102425845 A CN 2010102425845A CN 201010242584 A CN201010242584 A CN 201010242584A CN 101908477 B CN101908477 B CN 101908477B
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- polyimide film
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- polyimide
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Abstract
The invention belongs to the technical field of semiconductor memories, and particularly relates to a method for preparing a gate stack of a metallic nano crystal memory. The method comprises the following steps of: depositing a tunneling layer on a single crystal silicon substrate; spinning a layer of polyimide film on the tunneling layer; putting an anodic aluminum oxide template on the polyimide film serving as an etching mask; performing reactive ion etching on the polyimide film to form a polyimide mask; removing the anodic aluminum oxide template; depositing a layer of ultra-thin metal in the polyimide mask; removing the polyimide mask by adopting lift-off technology; depositing a barrier layer; and depositing a gate electrode. Because anodic aluminum oxide is used as a non-photolithographic mask plate, the formed nano crystal array has high density and uniform size distribution.
Description
Technical field
The invention belongs to the semiconductor memory technologies field, be specifically related to a kind of preparation method of gate stack of metallic nano crystal memory.
Background technology
In nanocrystalline nonvolatile memory field, mainly contain semiconductor nano and metallic nano crystal two class memories, wherein metallic nano crystal is owing to it has the higher density of states, has advantages such as better coupling, metal work function selectable range are big to enjoy favor with raceway groove near Fermi level.Yet the nanocrystalline acquisition of high desnity metal is the key of preparation high-performance metal nano-crystal memory.At present, the preparation of metallic nano crystal mainly obtains by rapid thermal annealing and two kinds of methods of template self assembly.The resulting metallic nano crystal uniformity of rapid thermal annealing method is relatively poor, and needs very high annealing temperature.The template self-assembly method mainly is to utilize protein companion crystalline substance or PS-b-PMMA[1] obtain nanocrystallinely as template, density is very high, and uniformity is also very good, but technology is very complicated.Employing anodic oxidation aluminium formwork proposed by the invention prepares metallic nano crystal, can solve the process complexity problem, and formed nanocrystalline being evenly distributed.Anodised aluminium is a kind of electrochemical process, be exactly in brief highly purified aluminium film through operations such as anodic oxidations, in pellumina, form high density (10
11Cm
-2), arrange orderly hexagon hole array, and can obtain the hole of the different-diameter and the degree of depth by control of process condition.
List of references
[1] D.?Shahrjerdi,?D.?I.?Garcia-Gutierrez,?and?S.?K.?Banerjee,?“Fabrication?of?Ni?Nanocrystal?Flash?Memories?Using?a?Polymeric?Self-Assembly?Approach”.?IEEE?Electron?Device?Letter.?,?28(9),?p793－796，2007。
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, the preparation method of the formed nanocrystalline gate stack of metallic nano crystal memory that is evenly distributed.
The preparation method of the gate stack of metallic nano crystal memory that the present invention proposes is to adopt anodic oxidation aluminium formwork as the reactive ion beam etching (RIBE) barrier layer, forms the nanohole array close with alumina formwork in polyimide film.After removing alumina formwork, the super thin metal of the method deposit one deck controllable thickness by sputter again.Then, behind the removal polyimide film, the nano crystal array that can form high density, is evenly distributed.This gate stack of metallic nano crystal memory structure specifically comprises: monocrystalline substrate, electric charge tunnel layer, metal nano crystal layer, electric charge barrier layer and gate electrode, and its step of preparation process is as follows:
1, be substrate with the monocrystalline silicon piece, deposit one layer charge tunnel layer on substrate is as adopting SiO
2/ Al
2O
3Double-decker tunnel layer, wherein SiO
2Be high-temperature thermal oxidation growth, Al
2O
3Be atomic layer deposition;
2, spin coating one deck polyimide film on the electric charge tunnel layer, THICKNESS CONTROL is in the 30-100 nanometer range;
3, anodic oxidation aluminium formwork is placed on the polyimide film, and makes closely contact between the two;
4, with alumina formwork as mask, polyimides is carried out reactive ion etching, make etching depth arrive the electric charge tunnel layer, thereby in polyimide film, form nanohole array, promptly obtain polyimide mask;
5, adopt the method for mechanical stripping or acid corrosion to remove alumina formwork;
6, adopt the super thin metal of method deposit one deck 3-10 nano thickness in the nano-pore of polyimide film of sputter, as the metal Ru or the palladium of ion beam sputtering 3-10 nanometer;
7, adopt the lift-off technology to remove polyimide film, carry out rapid thermal annealing 10-30 second at 600-800 ℃ then;
8, deposit one deck electric charge barrier layer is as atomic layer deposition HfAlO or HfLaO film;
9, adopt the reactive sputtering technology, the depositing metal gate electrode is as TaN.
Advantage of the present invention:
(1), adopt the etch mask of anodic oxidation aluminium formwork as polyimides, prepare the high density nano array structure, avoided the application bottleneck of common photoetching technique, that has also avoided simultaneously adopting electron beam lithography to bring is expensive.
(2), with the mask of polyimides template as the metal deposit, not only since this template easily in oxygen plasma atmosphere etching form, and it is also removed behind the organic solvent dissolution easily.
(3), owing to have highdensity, regular nanohole array in the anodic oxidation aluminium formwork, good characteristic such as therefore by after the figure transfer, formed metallic nano crystal also has same high density, be evenly distributed.
Description of drawings
Fig. 1: deposit one layer charge tunnel layer on silicon substrate.
Fig. 2: spin coating one deck polyimide film on tunnel layer.
Fig. 3: anodic oxidation aluminium formwork is placed on the polyimide film.
Fig. 4: polyimide film is carried out formed figure after the reactive ion etching.
Fig. 5: remove alumina formwork.
Fig. 6: deposit layer of metal on polyimide mask.
Fig. 7: adopt the lift-off technology to peel off polyimide mask.
Fig. 8: deposit one deck electric charge barrier layer.
Fig. 9: deposit layer of metal grid on electric charge barrier layer.
Embodiment
Below in conjunction with accompanying drawing, the present invention is carried out detailed explanation.
Step 1: with reference to Fig. 1, deposit one deck 201 is as the electric charge tunnel layer on substrate 200, and wherein 200 is monocrystalline silicon pieces; The 201st, the Al of atomic layer deposition
2O
3Film, thickness are 5～12 nanometers.
Step 2: with reference to Fig. 2, spin coating one deck 202 on 201, wherein 202 is polyimide films, thickness is the 30-100 nanometer.
Step 3: with reference to Fig. 3, be placed on 202 203, and make it tight contact, wherein 203 is alumina formworks, and the aperture of template is the 20-30 nanometer.
Step 4: with reference to Fig. 4, be that mask plate carries out reactive ion etching to 202 with 203, etching atmosphere is oxygen plasma.
Step 5:, adopt the method for mechanical stripping or acid corrosion to remove 203 with reference to Fig. 5.
Step 6: with reference to Fig. 6, the deep trouth surface sputtering deposit layer of metal 204 202, wherein 204 is metal Ru (Ru), thickness is the 3-10 nanometer.
Step 7:, adopt the lift-off technology to remove 202 with reference to Fig. 7.Then, carry out rapid thermal annealing 10-30 second at 600-800 ℃.
Step 8: with reference to Fig. 8, deposit one deck 205 is as the barrier layer, and wherein 205 is the HfLaO of atomic layer deposition, and thickness is the 20-30 nanometer.
Step 9: with reference to Fig. 9, reaction magnetocontrol sputtering deposit one deck 206 is as gate electrode, and wherein 206 is TaN, and thickness is the 100-200 nanometer.
Claims (5)
1. the preparation method of a gate stack of metallic nano crystal memory is characterized in that adopting anodic oxidation aluminium formwork as the reactive ion beam etching (RIBE) barrier layer, forms the nanohole array identical with alumina formwork in polyimide film; Remove alumina formwork, method deposit one layer thickness by sputter is the super thin metal of 3-10 nanometers again; Remove polyimide film then, the nano crystal array that promptly form high density, is evenly distributed.
2. preparation method according to claim 1 is characterized in that concrete steps are as follows:
(1) deposit one layer charge tunnel layer on the monocrystalline silicon piece substrate;
(2) spin coating one deck polyimide film on the electric charge tunnel layer, THICKNESS CONTROL is in the 30-100 nanometer range;
(3) anodic oxidation aluminium formwork is placed on the polyimide film, and makes closely contact between the two;
(4) with above-mentioned alumina formwork as mask, polyimides is carried out reactive ion etching, make etching depth arrive the electric charge tunnel layer, thereby in polyimide film, form nanohole array, promptly obtain polyimide mask;
(5) adopt the method for mechanical stripping or acid corrosion to remove alumina formwork;
(6) super thin metal of deposit one deck 3-10 nano thickness in the nano-pore of method in polyimide mask of employing sputter;
(7) adopt the lift-off technology to remove polyimide film, then 600-800 ℃ of thermal annealing 10-30 second;
(8) deposit one deck electric charge barrier layer;
(9) adopt reactive sputtering technology, depositing metal gate electrode.
3. preparation method according to claim 2 is characterized in that described deposit electric charge tunnel layer, is earlier with the high-temperature thermal oxidation SiO that grows
2, use atomic layer deposition method deposit Al then
2O
3
4. preparation method according to claim 2 is characterized in that described metallic nano crystal material selection Ru or Pd.
5. preparation method according to claim 2 is characterized in that described electric charge barrier layer selects the HfAlO or the HfLaO film of atomic layer deposition for use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102425845A CN101908477B (en) | 2010-08-02 | 2010-08-02 | Method for preparing gate stack of metallic nano crystal memory |
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|---|---|---|---|
| CN2010102425845A CN101908477B (en) | 2010-08-02 | 2010-08-02 | Method for preparing gate stack of metallic nano crystal memory |
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| CN101908477B true CN101908477B (en) | 2011-12-07 |
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| CN102168268A (en) * | 2011-03-02 | 2011-08-31 | 复旦大学 | Preparation method of metal nanocrystal |
| CN104201148A (en) * | 2014-07-31 | 2014-12-10 | 上海华力微电子有限公司 | Method for forming pores in low-K dielectric layer |
| CN105088304A (en) * | 2015-08-10 | 2015-11-25 | 华南师范大学 | Method for preparing an ordered nanodot array by one-step template method |
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| CN100495736C (en) * | 2007-04-26 | 2009-06-03 | 复旦大学 | Process for producing TiO*/metallic array electrode with ordered nano-structure |
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