CN104528634A - Side wall forming and manufacturing method for nanometer structure - Google Patents
Side wall forming and manufacturing method for nanometer structure Download PDFInfo
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Abstract
The invention discloses a side wall forming and manufacturing method for a nanometer structure. According to the method, nanometer points and wire structures of any size and smaller than 5 nm can be manufactured manually. According to a manufacturing method of the nanometer and micrometer structure low in price, compared with a traditional manufacturing method, the side wall forming method for the nanometer structure does not need to depend on expensive electron beam exposure equipment or high-resolution deep ultra-violet lithography equipment, the method for generating the nanometer structure low in price is realized, and the method can be widely applied to the nanometer fundamental science and the application research and can meet the requirement for manufacturing the nanometer and micrometer structure in industrial production. According to the manufacturing range of the wide nanometer and micrometer structure, the nanometer and micrometer structure prepared through the side wall forming method for the nanometer structure depends on the thickness of a deposited side wall hard mask material, and accordingly the nanometer and micrometer structure of any size can be manufactured by utilizing the method.
Description
Technical field
The present invention relates to field of nanometer technology, particularly a kind of sidewall forming manufacturing method of nanostructured.
Background technology
Nanoscale science and technology is a Comprehensive Science relating to the subject crossing such as physics, chemistry, materialogy, microelectronics, biology and medical science.Because nano material shows special quantum size effect under microsize, nanoscale science and technology causes in theory extensively to be noted and experiencing development at a high speed in application.
Nanostructured has challenging research field in current scientific development forward position.At nano material emerging in a large number and device while the fermentation such as electronic device, integrated circuit, biomedicine, national defence show unprecedented application prospect, reduce that to receive micron manufacturing cost be the prerequisite of nano-device industrial applications.Along with the physical size of device constantly reduces, it is also proposed higher requirement to device fabrication condition, traditional material, technique all will meet with technical bottleneck.Industrialized nano structure manufacture nearly all at present all will depend on the very expensive semiconductor deep-UV lithography of price (Deep-UV Photolithograph), and the technology of these advanced persons all needs to use photo etched mask technology.Electron beam exposure photoetching (Electron Lithography Beam, EBL) does not need mask, but manufacture process is consuming time long, is not suitable for heavy industrialization application.At small scale nano-device manufacture view, use the Xe light source that wavelength is the shortest, owing to being subject to the interference of light, the impact of diffraction, the minimum nanostructured made also can only reach 12nm.Although the structure of the minimum dimension 5nm that state-of-the-art X-ray lithography technology can be made, because X-ray penetration power is extremely strong, be very difficult when using X-ray to do mask.The most important thing is that the equipment price needed for these advanced technologies is all very expensive, can accomplish that the litho machine price of tens above structures of nanometer all will reach several ten million dollars.There is problem that is expensive and size manufacture bottleneck in existing device, method.
Existing nano wire forming method uses individual layer mask and chemical vapour deposition technique to deposit hard mask.Utilize the mask of single-layer lithography glue, after exposure is fixing, their bottom inevitably occurs the instep structure extended making definition nanoscale become very difficult.Chemical vapour deposition technique deposits the method for hard mask simultaneously, due to the inhomogeneities of chemical gaseous phase depositing process, is difficult to ensure the uniform thickness distribution on sidewall of hard mask.
Summary of the invention
Technical problem to be solved by this invention is the sidewall forming manufacturing method overcoming the deficiencies in the prior art and provide a kind of nanostructured, the method is without the need to relying on expensive lithographic exposure apparatus, the nanostructure size of film, completely by the THICKNESS CONTROL of sidewall hard mask material, manually can manufacture arbitrary dimension and the nano dot and the line structure that are less than 5nm like this.
The present invention is for solving the problems of the technologies described above by the following technical solutions:
According to the sidewall forming manufacturing method of a kind of nanostructured that the present invention proposes, comprise the following steps:
Step one, provide substrate;
Step 2, over the substrate deposit film;
Step 3, side wall construction are shaped, and are specially:
301, adopt sol evenning machine spin coating photoresist on the membrane, front baking is carried out to photoresist;
302, adopt magnetron sputtering, electron beam evaporation on a photoresist, metal or oxide material that chemical vapour deposition (CVD) thickness is 5 nanometer ~ 20 nanometers;
303, spin coating photoresist on described metal or oxide material, utilizes litho machine to carry out photoetching after carrying out front baking, adopt washed with de-ionized water after development to photoresist, and dries up the side wall construction obtained perpendicular to metal or oxide material with nitrogen;
304, reactive ion etching or ion beam etching is adopted to etch metal or oxide material;
305, with metal or oxide material for mask, adopt reactive ion etching to etch the photoresist be positioned at above metal or oxide material, form nano strip sidewall;
Step 4, employing technique for atomic layer deposition deposit hard mask nano material;
Step 5, employing ion beam etching etch hard mask nano material, expose photoresist;
Step 6, employing acetone stripping photoresist, to form nanometer sidewall figure;
Step 7, with described nanometer sidewall figure for mask, adopt ion beam etching film;
Step 8, employing wet etching or chemical vapour deposition (CVD) etching hard mask material obtain the nano strip sidewall of thin-film material.
As the scheme that the sidewall forming manufacturing method of a kind of nanostructured of the present invention is further optimized, described hard mask material is Al
2o
3or Si
3n
4or RuO or a-Carbon.
As the scheme that the sidewall forming manufacturing method of a kind of nanostructured of the present invention is further optimized, in described step 2, the method for deposit film is magnetron sputtering or electron beam evaporation or chemical vapour deposition (CVD) or collosol and gel or spraying process.
As the scheme that the sidewall forming manufacturing method of a kind of nanostructured of the present invention is further optimized, the method depositing hard mask nano material in described step 4 is Atomic layer deposition method or chemical gaseous phase depositing process.
As the scheme that the sidewall forming manufacturing method of a kind of nanostructured of the present invention is further optimized, further comprising the steps of after step 8:
Step 9, employing sol evenning machine spin coating photoresist on substrate and nano strip, utilize litho machine to carry out photoetching, be immersed in deionized water and clean after development, and dry up the side wall construction obtained perpendicular to substrate direction with nitrogen after front baking;
Step 10, employing technique for atomic layer deposition or chemical vapor deposition hard mask material;
The photoresist that step 11, exposure hard mask material are covered: utilize ion beam etching to etch hard mask material, and expose photoresist;
Step 12, employing acetone stripping photoresist, form the nano thread structure of hard mask material perpendicular to substrate direction;
Step 13, to etch on thin-film material, form the nanostructured that hard mask material coexists perpendicular to the nano wire in substrate direction and the nano dot of thin-film material;
Step 14, employing wet etching or chemical vapour deposition (CVD) etching peel off hard mask material, obtain the nano dot sidewall of thin-film material.
The present invention adopts above technical scheme compared with prior art, has following technique effect:
(1) brand-new nanometer Points And lines manufacture method: the sidewall forming manufacturing method of the nanostructured of invention bilayer mask and technique for atomic layer deposition is a kind of method that brand-new nano-device manufactures.The method manually can manufacture arbitrary dimension and be less than nano dot and the line structure of 5nm.
(2) manufacture method of the nanometer micrometer structure of low price: compared with traditional manufacture method, the method of " shaping of sidewall nanostructured ", without the need to relying on expensive electron beam exposure apparatus and high-resolution deep-UV lithography equipment, accomplish nanostructured production method at a low price, the demand in nanometer basic science and application study and suitability for industrialized production, nanometer micrometer structure manufactured can be widely used in.
(3) wide nanometer micrometer structure manufactures scope: because nanometer micrometer structure prepared by sidewall nanostructured manufacturing process depends on the thickness of the sidewall hard mask material of deposition, profit can manufacture the nanometer micrometer structure of arbitrary dimension in this way like this.
(4) manufacture method with the following nanostructured of large area 10 nanometer can uniquely be manufactured on a large scale at present: in current low-dimensional scientific research, physical size amount, usually at nanoscale, is often less than 5nm.Even if use advanced electron beam lithography, nanoscale also can only reach 12nm.Like this, the method that new device making method-sidewall nanostructured is shaped uniquely at present manufactures the manufacture method being less than 10 nanostructureds.
Accompanying drawing explanation
Fig. 1 is that side wall construction forms schematic diagram.
Fig. 2 is the schematic diagram of ion beam etching photoresist and metal.
Fig. 3 is reactive ion etching (RIE) anisotropic etching photoresist schematic diagram.
Fig. 4 is technique for atomic layer deposition deposition hard mask material schematic diagram.
Fig. 5 is the Other substrate materials schematic diagram that exposure hard mask material is covered.
Fig. 6 is the formation schematic diagram of hard mask nanostructured.
Fig. 7 is the nanostructured etching schematic diagram of thin-film material.
Fig. 8 peels off hard mask material to form nano strip sidewall schematic diagram.
Fig. 9 forms side wall construction shaping schematic diagram.
Figure 10 is hard mask material deposition schematic diagram.
Figure 11 is the photoresist schematic diagram exposing hard mask material covering.
Figure 12 is the formation schematic diagram of hard mask material nanostructured.
Figure 13 is the nanostructured etching schematic diagram of thin-film material.
Figure 14 is the formation schematic diagram of film nano point side wall construction.
Reference numeral in figure is interpreted as: 1 is substrate, and 2 is film, and 3 is photoresist, and 4 is metal, and 5 is hard mask nano material, and 6 is nano strip sidewall, and 7 is nano dot sidewall.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in further detail:
Fig. 1-Fig. 8 is the forming process of nano strip sidewall, if Fig. 1 is that side wall construction forms schematic diagram.Fig. 2 is the schematic diagram of ion beam etching photoresist and metal.Fig. 3 is reactive ion etching (RIE) anisotropic etching photoresist schematic diagram.Fig. 4 is technique for atomic layer deposition deposition hard mask material schematic diagram.Fig. 5 is the Other substrate materials schematic diagram that exposure hard mask material is covered.Fig. 6 is the formation schematic diagram of hard mask nanostructured.Fig. 7 is the nanostructured etching schematic diagram of thin-film material.Fig. 8 peels off hard mask material to form nano strip sidewall schematic diagram.Detailed process following steps:
A sidewall forming manufacturing method for nanostructured, comprises the following steps:
Step one, provide substrate 1;
Step 2, over the substrate deposit film 2;
Step 3, side wall construction are shaped, and are specially:
301, on described film 2, adopt sol evenning machine spin coating photoresist 3, front baking is carried out to photoresist 3;
302, on photoresist 3, adopt magnetron sputtering, electron beam evaporation, metal 4 or oxide material that chemical vapour deposition (CVD) thickness is 5 nanometer ~ 20 nanometers;
303, spin coating photoresist on described metal 4 or oxide material, utilizes litho machine to carry out photoetching after carrying out front baking, adopt washed with de-ionized water after development to photoresist, and dries up the side wall construction obtained perpendicular to metal or oxide material with nitrogen; As Fig. 1;
304, reactive ion etching or ion beam etching is adopted to etch metal or oxide material; As Fig. 2;
305, with metal or oxide material for mask, adopt reactive ion etching to etch the photoresist be positioned at above metal or oxide material, form nano strip sidewall; As Fig. 3;
Step 4, employing technique for atomic layer deposition deposit hard mask nano material 5; As Fig. 4;
Step 5, employing ion beam etching etch hard mask nano material 5, expose photoresist; As Fig. 5;
Step 6, employing acetone stripping photoresist, to form nanometer sidewall figure; As Fig. 6;
Step 7, with described nanometer sidewall figure for mask, adopt ion beam etching film; As Fig. 7;
Step 8, employing wet etching or chemical vapour deposition (CVD) etching hard mask material obtain the nano strip sidewall 6 of thin-film material, as Fig. 8.
Described hard mask material is Al
2o
3or Si
3n
4or RuO or a-Carbon.In described step 2, the method for deposit film is magnetron sputtering or electron beam evaporation or chemical vapour deposition (CVD) or collosol and gel or spraying process.The method depositing hard mask nano material in described step 4 is Atomic layer deposition method or chemical gaseous phase depositing process.
Fig. 9-Figure 14 is the forming process of nano dot.Fig. 9 forms side wall construction shaping schematic diagram.Figure 10 is hard mask material deposition schematic diagram.Figure 11 is the photoresist schematic diagram exposing hard mask material covering.Figure 12 is the formation schematic diagram of hard mask material nanostructured.Figure 13 is the nanostructured etching schematic diagram of thin-film material.Figure 14 is the formation schematic diagram of film nano point side wall construction.
Further comprising the steps of after step 8:
Step 9, employing sol evenning machine spin coating photoresist on substrate and nano strip, utilize litho machine to carry out photoetching, be immersed in deionized water and clean after development, and dry up the side wall construction obtained perpendicular to substrate direction with nitrogen after front baking; As shown in Figure 9;
Step 10, employing technique for atomic layer deposition or chemical vapor deposition hard mask material; As shown in Figure 10;
The photoresist that step 11, exposure hard mask material are covered: utilize ion beam etching to etch hard mask material, and expose photoresist; As shown in figure 11;
Step 12, employing acetone stripping photoresist, form the nano thread structure of hard mask material perpendicular to substrate direction; As shown in figure 12;
Step 13, to etch on thin-film material, form the nanostructured that hard mask material coexists perpendicular to the nano wire in substrate direction and the nano dot of thin-film material; As shown in figure 13;
Step 14, employing wet etching or chemical vapour deposition (CVD) etching peel off hard mask material, obtain the nano dot sidewall 7 of thin-film material, as shown in figure 14.
example 1, the sidewall nanostructured manufacturing process of 10 nano-ZnO nano strips
The first step, ZnO film deposits: the ZnO film depositing 100 nanometer thickness in Si/SiO2 substrate by the method for pulsed laser deposition (PLD) (Coherent 350 laser instrument), optimum condition: temperature: 500 DEG C, oxygen pressure: 30Pa, laser energy: 300mJ, frequency: 10Hz, sedimentation time: 15min.
Second step, side wall construction is shaped:
1. utilize sol evenning machine spin coating photoresist (photoresist is the RZJ-304 positive photoresist that the auspicious red-face role in Suzhou produces): slow-speed of revolution 500rpm 5s, high rotating speed 3000rpm 20s; Drying glue: front baking 100 DEG C of 120s, then utilizes electron-beam evaporation a layer thickness to be 20 nano metal Cu.Before starting evaporation, the Kaufman ion source purging system utilizing electron beam evaporation system to carry cleans sample surfaces, end vacuum: 8 × 10
-4, Kaufman ion source cleans: Ar operating pressure 2 × 10
-2, discharge voltage 68V, heater current 8A, accelerating potential 150V, line voltage 500V, scavenging period 60s.Then open scanning, regulate high pressure to select 8KV, regulate gun filament electric current 0.4A, regulate line 300mA, evaporation rate is greatly about 0.2nm/s, and evaporation a layer thickness is the metallic copper of 20nm.
2. utilize sol evenning machine second time spin coating photoresist: utilize sol evenning machine spin coating photoresist (photoresist is the RZJ-304 positive photoresist that the auspicious red-face role in Suzhou produces): slow-speed of revolution 500rpm 5s, high rotating speed 3000rpm 20s; Drying glue: front baking 100 DEG C of 120s, the litho machine then utilizing ABM company to produce carries out photoetching: exposure 8s, light intensity 15mw/cm
2, then developing, (immersed by sample in the RZX-3038 positivity developer solution of the auspicious red-face role's product in Suzhou, developing time is 10s, then washed with de-ionized water is used rapidly, and dry up with nitrogen, the effect of basis of microscopic observation photoetching, post bake: the side wall construction 100 DEG C of 5min) obtaining Y-direction.
3. the Ni metal exposed after utilizing ion beam etching (IBE, model IBE-150B) to etch photoetching development.Vacuum: 5.0
10
-4, sample stage temperature: 6 DEG C, incidence angle: θ=15 °, Ar flow MFC1:4.16, cathode current: 13.0A, anode voltage: 60V, screen step voltage: 500V, accelerating potential: 300V, in and electric current: 10.2A, biased: 1.20, input voltage: 220V, etch period 90 seconds.
4. utilize metallic copper mask, adopt reactive ion etching to etch photoresist residual above metallic copper mask, power: 450w, pressure: 225mtorr, oxygen flow: 100sccm, the working time: 4min, forms side wall construction on the photoresist under metallic copper mask simultaneously.
3rd step, hard mask material deposits: utilize technique for atomic layer deposition (Atom Layer Deposition (ALD) model: Savannah 100, Cambridge Nanotech) to deposit 10 nanometer thickness Al
2o
3hard mask material, presoma burst length: 0.03s, open-assembly time: 5s, cleaning time: 30s, temperature: 150 DEG C, cycle-index: 80 times.
4th step, exposes the Other substrate materials that hard mask material is covered: ion beam etching (IBE, model IBE-150B) top and bottom hard mask material Al
2o
3part.Vacuum: 5.0
10
-4, sample stage temperature: 6 DEG C, incidence angle: θ=15 °, Ar flow MFC1:4.16, cathode current: 13.0A, anode voltage: 60V, screen step voltage: 500V, accelerating potential: 300V, in and electric current: 10.2A, biased: 1.20, input voltage: 220V, etch period 60 seconds.
5th step, the formation of hard mask nanostructured: the sample taking-up after the 4th step etching terminates is immersed in ultrasonic 5min in acetone, stripping photoresist, and then washed with de-ionized water 3 times, nitrogen dries up the nanostructured obtaining 10 nanometer hard mask materials.
6th step, the nanostructured etching of thin-film material: utilize Al2O3 as the hard mask material of ion beam etching (IBE) ZnO material.Vacuum: 5.0
10
-4sample stage temperature: 6 DEG C, incidence angle: θ=15 °, Ar flow MFC1:4.16, cathode current: 13.0A, anode voltage: 60V, screen step voltage: 500V, accelerating potential: 300V, in and electric current: 10.2A, biased: 1.20, input voltage: 220V, etch period forms 10 nano-ZnOs/Al in 300 seconds
2o
3nano thread structure.
7th step, wet method peels off hard mask material: the sample taking-up after the 6th step etching terminates is immersed in photoresist developing liquid B, soaks 10min), photoresist developing vacuole 3 minutes, wet etching Al
2o
3, then rinsed with deionized water three times, obtains 10 nano-scale ZnO nano bars.
example 2, the sidewall nanostructured manufacturing process of 10 nano-ZnO nano dots
It is article consistent that the first step to the 7th step and example 1 method obtains 10 nano-scale ZnO nanos
8th step, side wall construction is shaped: utilize sol evenning machine spin coating photoresist (photoresist is the RZJ-304 positive photoresist that the auspicious red-face role in Suzhou produces): slow-speed of revolution 500rpm 5s, high rotating speed 3000rpm 20s; Drying glue: front baking 100 DEG C of 120s, utilizes the litho machine of ABM company to carry out photoetching: exposure 8s, light intensity 15mw/cm
2, then developing, (immersed by sample in the RZX-3038 positivity developer solution of the auspicious red-face role's product in Suzhou, developing time is 10s, then washed with de-ionized water is used rapidly, and dry up with nitrogen, the effect of basis of microscopic observation photoetching, post bake: the side wall construction 100 DEG C of 5min) obtaining X-direction.
9th step, hard mask material deposits: utilize technique for atomic layer deposition (Atom Layer Deposition (ALD) model: Savannah 100, Cambridge Nanotech) to deposit 10 nanometer thickness Al
2o
3hard mask material, presoma burst length: 0.03s, open-assembly time: 5s, cleaning time: 30s, temperature: 150 DEG C.Cycle-index: 80 times.
Tenth step, exposes the Other substrate materials that hard mask material is covered: ion beam etching (IBE, model IBE-150B) top and bottom hard mask material Al
2o
3part.Vacuum: 5.0
10
-4, sample stage temperature: 6 DEG C, incidence angle: θ=15 °, Ar flow MFC1:4.16, cathode current: 13.0A, anode voltage: 60V, screen step voltage: 500V, accelerating potential: 300V, in and electric current: 10.2A, biased: 1.20, input voltage: 220V, etch period 60 seconds.
11 step, the formation of hard mask nanostructured: the sample taking-up after the 4th step etching terminates is immersed in ultrasonic 5min in acetone, stripping photoresist, and then washed with de-ionized water 3 times, nitrogen dries up the nanostructured obtaining 10 nanometer hard mask materials.
12 step, the nanostructured etching of thin-film material: utilize Al2O3 as the hard mask material of ion beam etching (IBE) ZnO material.Vacuum: 5.0
10
-4, sample stage temperature: 6 DEG C, incidence angle: θ=15 °, Ar flow MFC1:4.16, cathode current: 13.0A, anode voltage: 60V, screen step voltage: 500V, accelerating potential: 300V, in and electric current: 10.2A, biased: 1.20, input voltage: 220V, etch period 300 seconds, forms 10 nano-ZnOs/Al
2o
3nano thread structure.
13 step, wet method peels off hard mask material: the sample taking-up after the 6th step etching terminates is immersed in photoresist developing liquid B, soaks 10min), photoresist developing vacuole 3 minutes, wet etching Al
2o
3, rinsed with deionized water three times, obtains 10 nano-scale ZnO nano points.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And these belong to connotation of the present invention the apparent change of extending out or variation still belong to protection scope of the present invention.
Claims (5)
1. a sidewall forming manufacturing method for nanostructured, is characterized in that, comprise the following steps:
Step one, provide substrate;
Step 2, over the substrate deposit film;
Step 3, side wall construction are shaped, and are specially:
301, adopt sol evenning machine spin coating photoresist on the membrane, front baking is carried out to photoresist;
302, adopt magnetron sputtering, electron beam evaporation on a photoresist, metal or oxide material that chemical vapour deposition (CVD) thickness is 5 nanometer ~ 20 nanometers;
303, spin coating photoresist on described metal or oxide material, utilizes litho machine to carry out photoetching after carrying out front baking, adopt washed with de-ionized water after development to photoresist, and dries up the side wall construction obtained perpendicular to metal or oxide material with nitrogen;
304, reactive ion etching or ion beam etching is adopted to etch metal or oxide material;
305, with metal or oxide material for mask, adopt reactive ion etching to etch the photoresist be positioned at above metal or oxide material, form nano strip sidewall;
Step 4, employing technique for atomic layer deposition deposit hard mask nano material;
Step 5, employing ion beam etching etch hard mask nano material, expose photoresist;
Step 6, employing acetone stripping photoresist, to form nanometer sidewall figure;
Step 7, with described nanometer sidewall figure for mask, adopt ion beam etching film;
Step 8, employing wet etching or chemical vapour deposition (CVD) etching hard mask material obtain the nano strip sidewall of thin-film material.
2. the sidewall forming manufacturing method of a kind of nanostructured according to claim 1, is characterized in that, described hard mask material is Al
2o
3or Si
3n
4or RuO or a-Carbon.
3. the sidewall forming manufacturing method of a kind of nanostructured according to claim 1, is characterized in that, in described step 2, the method for deposit film is magnetron sputtering or electron beam evaporation or chemical vapour deposition (CVD) or collosol and gel or spraying process.
4. the sidewall forming manufacturing method of a kind of nanostructured according to claim 1, is characterized in that, the method depositing hard mask nano material in described step 4 is Atomic layer deposition method or chemical gaseous phase depositing process.
5. the sidewall forming manufacturing method of a kind of nanostructured according to claim 1, is characterized in that, further comprising the steps of after step 8:
Step 9, employing sol evenning machine spin coating photoresist on substrate and nano strip, utilize litho machine to carry out photoetching, be immersed in deionized water and clean after development, and dry up the side wall construction obtained perpendicular to substrate direction with nitrogen after front baking;
Step 10, employing technique for atomic layer deposition or chemical vapor deposition hard mask material;
The photoresist that step 11, exposure hard mask material are covered: utilize ion beam etching to etch hard mask material, and expose photoresist;
Step 12, employing acetone stripping photoresist, form the nano thread structure of hard mask material perpendicular to substrate direction;
Step 13, to etch on thin-film material, form the nanostructured that hard mask material coexists perpendicular to the nano wire in substrate direction and the nano dot of thin-film material;
Step 14, employing wet etching or chemical vapour deposition (CVD) etching peel off hard mask material, obtain the nano dot sidewall of thin-film material.
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