CN104051043B - 3D type PIN structure alpha irradiation battery and manufacturing method thereof - Google Patents
3D type PIN structure alpha irradiation battery and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a 3D type PIN structure alpha irradiation battery and a manufacturing method of the 3D type PIN structure alpha irradiation battery. The 3D type PIN structure alpha irradiation battery and the manufacturing method mainly solve the problems that an existing alpha irradiation battery is low in energy conversion rate and output power. The manufacturing method includes the implementation steps of sequentially growing an N type lightly-doped 4H-SiC epitaxial layer and a P type highly-doped 4H-SiC epitaxial layer on a washed 4H-SiC substrate in an epitaxial mode, forming ohmic contact electrodes on the non-epitaxial back face of the P type highly-doped epitaxial layer and the non-epitaxial back face of the SiC substrate through deposition, conducting photoetching on the P type ohmic contact electrodes to obtain groove windows, conducting etching to obtain grooves, and placing alpha irradiation sources in the grooves to obtain the 3D type PIN structure alpha irradiation battery. The 3D type PIN structure alpha irradiation battery manufactured according to the method has the advantages that the contact area between the alpha irradiation battery and the alpha irradiation sources is large, the nuclear raw material utilization rate and the energy collection rate are high, and the battery output current and the battery output voltage are large; the 3D type PIN structure alpha irradiation battery can unceasingly supply power for miniature circuits or can supply power on the occasions where long-time power supply is needed but not unmanned.
Description
Technical field
The invention belongs to microelectronic, it is related to semiconductor device structure and preparation method, specifically a kind of carbonization
PIN-type alpha irradiation battery of silicon substrate and preparation method thereof, can be used for the fine circuit such as minute mechanical and electrical system and Aero-Space, deep-sea,
Polar region etc. need to power and unattended occasion for a long time.
Technical background
With people for low-power consumption, long-life, high reliability and small size power supply unit demand, and to nuke rubbish
The concern processing, minisize nuclear battery becomes to receive much concern.Minisize nuclear battery can be used to solve miniature tube due to its prominent feature
Pipeline robot, implantable MEMS, wireless sensor node network, artificial cardiac pacemaker and Portable movable electronic product etc.
Long-term powerup issue.And be expected to replace solaode and thermoelectric (al) type radioisotope battery, in space flight and aviation field
Solve the long-term powerup issue of micro-/Nano satellite, deep space unmanned probing device and ion propeller etc..
Nineteen fifty-three is studied by Rappaport and finds, using beta produced by isotope decay (β-Particle) ray
Electron-hole pair can be produced in quasiconductor, this phenomenon is then referred to as β-Voltaic Effect.Nineteen fifty-seven, Elgin-Kidde
First β-Voltaic Effect is used in power supply supply side, successfully produces first radioisotope micro battery β-Voltaic
Battery.From 2006, with the progress of semiconductor material with wide forbidden band SiC technology of preparing and Technology, occur in that and be based on
The relevant report of the radioisotope micro battery of SiC.
The Schottky junction type based on SiC being proposed by Zhang Lin, Guo Hui et al. is disclosed in Chinese patent CN 101325093A
Nuclear battery.Because in this schottky junction nuclear battery, schottky contact layer covers whole cell area, incoming particle reaches device table
Behind face, all can be stopped by schottky contact layer, only some particles can enter device inside, and enters the particle of depletion region
Just the output of battery can be contributed.Therefore, the nuclear battery projectile energy loss of this structure is big, energy conversion effect
Rate is relatively low.
Document " Demonstration of a 4H SiC betavoltaic cell " describes by USA New York
The C.I.Tomas of Cornell university, M.V.S.Chandrashekhar, Hui Li et al. propose carborundum PN junction formula nuclear power
Pond.The substrate that this structure adopts is the highly doped SiC substrate of p-type, and the existing process in its Grown epitaxial layer does not become
Ripe, therefore, it is easily introduced surface defect, battery leakage current is big, and energy conversion rate is relatively low.
Document " Demonstration of a tadiation resistant, hight efficiency SiC
Betavoltaic " describes by the C.J.Eiting of New Mexico Qynergy Corporation,
V.Krishnamoorthy and S.Rodgers, T.George et al. propose carborundum p-i-n junction formula nuclear battery jointly, such as Fig. 1
Shown.This PIN nuclear battery is followed successively by from top to bottom, radioactive source 7, p-type Ohm contact electrode 6, the highly doped SiC layer of p-type 4, p-type
SiC layer 3, intrinsic i layer 2, the highly doped SiC substrate of N-shaped 1 and N-type Ohm contact electrode 5.In this structure, only in depletion layer and
The raw carrier of irradiation in its neighbouring minority diffusion length can be collected.And, for avoiding Ohm contact electrode to stop
Incident ion, p-type Ohmic electrode is made in a corner of device so that giving birth to carrier from p-type Ohmic electrode irradiation farther out
Transport process is combined, is reduced energy transformation ratio, reduced the output current of battery.
Content of the invention
Present invention aims to the deficiency of above-mentioned prior art, propose a kind of 3D formula PIN structural alpha irradiation battery and
Its preparation method, to eliminate the barrier effect of the high-energyα-particle that metal electrode gives off to αsource, increases αsource simultaneously
With the contact area of quasiconductor, improve the utilization rate of αsource, thus improving output current and the output voltage of battery.
The technical scheme is that and be achieved in that：
One. the 3D formula PIN structural alpha irradiation battery of the present invention, including：PIN junction and αsource, PIN junction is from bottom to top successively
For N-type Ohm contact electrode 5, N-type highly doped 4H-SiC substrate 1 ', the low-doped epitaxial layer of N-type 8, the highly doped epitaxial layer 4 ' of p-type
With p-type Ohm contact electrode 6 it is characterised in that：It is provided with least two grooves 9, αsource 7 ' is placed on this in described PIN junction
In groove 9, to realize high-energyα-particle is made full use of.
Preferably, the americium element that described αsource 7 ' is 241 using atomic mass, i.e. Am241.
Preferably, the plutonium element that described αsource 7 ' is 238 using atomic mass, i.e. Pu238.
Preferably, depth h of described groove 9 meets m+q<h<M+n+q, wherein m are the thickness of the highly doped epitaxial layer 4 ' of p-type
Degree, n is the thickness of the low-doped epitaxial layer of N-type 8, and q is the thickness of p-type Ohm contact electrode 6.
Preferably, the width L of described groove 9 meets L 2g, wherein, the high-energyα-particle that g discharges for αsource 7 ' exists
Average incident depth in αsource, is Am for αsource241, its value is：G=7.5 μm, for αsource it is
Pu238, its value is：G=10 μm.
Preferably, spacing d of described two neighboring groove 9 meets d >=i, wherein, the height that i discharges for αsource 7 '
Energy average incident depth in 4H-SiC for the alpha-particle, is Am for αsource241, its value is：I=10 μm, α is put
Source of penetrating is Pu238, its value is：I=18.2 μm.
Preferably, it is l x 10 that described substrate 1 ' adopts doping content18cm-3N-type 4H-SiC, the highly doped extension of p-type
Layer 4 ' and the low-doped epitaxial layer of N-type 8 are the 4H-SiC of extension, and the wherein doping content of the highly doped epitaxial layer 4 ' of p-type is 1x
1019～5x 1019cm-3, the doping content of the low-doped epitaxial layer of N-type 8 is 1x 1015～2x 1015cm-3.
Two. the preparation method of the present invention comprises the following steps：
1) clean：SiC sample is carried out, to remove surface contaminant；
2) grow the low-doped epitaxial layer of N-type：Using chemical vapor deposition CVD SiC sample surface extension after cleaning
One layer of doping content of growth is 1x 1015～2x 1015cm-3, thickness is 5～10 μm of the low-doped epitaxial layer of N-type；
3) the highly doped epitaxial layer of growing P-type：Using chemical vapor deposition CVD in N-type low-doped epi-layer surface extension
One layer of doping content of growth is 1x 1019～5x 1019cm-3, thickness is 1～2 μm of the highly doped epitaxial layer of p-type；
4) deposit p-type Metal contact electrode：Electron-beam vapor deposition method is utilized to deposit thick layer in the highly doped epi-layer surface of p-type
Spend the Ni metal level for 300nm, the mask as etching groove and p-type metal ohmic contact；Served as a contrast in SiC using same method
The back side deposition thickness of the non-extension in bottom is the Ni metal level of 300nm, as N-type Ohm contact electrode；Nitrogen atmosphere at 1100 DEG C
Middle short annealing 3 minutes；
5) litho pattern：Position according to nuclear battery groove is fabricated to reticle；Ni layer on surface of metal spin coating in deposit
One layer of photoresist, carries out electron beam exposure using reticle to photoresist, forms corrosion window；To the Ni metal at corrosion window
Layer is corroded, and exposes the highly doped epitaxial layer of p-type, obtains p-type Ohm contact electrode and trench etching window；
6) etching groove：Using inductively coupled plasma ICP lithographic technique, the p-type exposed in etching groove window is high
Carve on doped epitaxial layer for placing αsource, depth is 6.5～12 μm, width is 5～14 μm, spacing is 12～25 μm
At least two grooves；
7) place αsource：Method using depositing or smear, places αsource in the trench, obtains 3D formula PIN junction
Structure alpha irradiation battery.
The present invention compared with prior art has the advantage that：
1. αsource is placed in groove so that the high-energyα-particle that αsource produces is emitted directly toward PIN junction the present invention
Space-charge region, reduces the energy loss of high-energyα-particle, thus improve collection of energy rate；
2. the present invention due to groove width be not more than αsource release high-energyα-particle averagely enter in αsource material
Penetrate the twice of depth, significantly reduce energy attenuation within αsource for the high-energyα-particle, improve collection of energy rate；
3. the present invention due to the energy gap using backing material 4H-SiC bigger than the energy gap of traditional Si, Flouride-resistani acid phesphatase is special
Property more preferably, the damage to device for the high-energyα-particle can be reduced, improve the running voltage of battery, extend making of battery simultaneously
Use the life-span.
Brief description
Fig. 1 is the schematic cross-section of existing PIN nuclear battery；
Fig. 2 is the schematic cross-section of 3D formula PIN structural alpha irradiation battery of the present invention；
Fig. 3 is the schematic flow sheet that the present invention makes 3D formula PIN structural alpha irradiation battery.
Specific embodiment
Reference Fig. 2, the irradiation battery of the present invention, including：PIN junction, groove 9 and αsource 7 ', PIN junction from bottom to top according to
Secondary be, N-type Ohm contact electrode 5, N-type highly doped 4H-SiC substrate 1 ', the low-doped epitaxial layer of N-type 8, the highly doped epitaxial layer of p-type
4 ' and p-type Ohm contact electrode 6.Wherein, the low-doped epitaxial layer of N-type 8 is grown on the silicon face of N-type highly doped 4H-SiC substrate 1 '
On, p-type highly doped 4H-SiC epitaxial layer 4 ' is grown on N-type low-doped 4H-SiC epitaxial layer 8, and p-type Ohm contact electrode 6 deposits
On p-type highly doped 4H-SiC epitaxial layer 4 ', using W metal, its thickness is 300nm, and back side N-type Ohm contact electrode 5 deposits
In the dorsal part of N-type highly doped 4H-SiC substrate 1 ', using W metal, its thickness is 300nm, constitutes PIN junction；PIN junction sets
There are at least two grooves 9, its depth h meets m+q<h<M+n+q, m are the thickness of the highly doped epitaxial layer 4 ' of p-type, and n is N-type low-mix
The thickness of miscellaneous epitaxial layer 8, q is the thickness of p-type Ohm contact electrode 6, and its width L meets L 2g, and g discharges for αsource 7 '
Average incident depth in αsource for the high-energyα-particle, is Am for αsource241, its value is：G=7.5 μm, for
αsource is Pu238, its value is：G=10 μm, and spacing d of two neighboring groove 9 meets d >=i, for αsource is
Am241, its value is：I=10 μm, be Pu for αsource238, its value is：I=18.2 μm；αsource 7 ' is placed
In groove 9.
Battery in working order under, it is highly doped that most of high-energyα-particle of radiating from αsource is emitted directly toward p-type
Epitaxial layer 4 ' and the space-charge region of the low-doped epitaxial layer of N-type 8 near interface, and then excite carrier, form output current.
With reference to Fig. 3, the method that the present invention makes 3D formula PIN structural alpha irradiation battery provides following three embodiment：
Embodiment 1, preparing αsource is Am241, there is the 3D formula PIN structural alpha irradiation battery of two grooves.
Step 1:Cleaning 4H-SiC print, to remove surface contaminant, such as shown in Fig. 3 (a).
(1.1) doping content is l x 1018cm-3Doped n-type 4H-SiC substrate print in NH4OH+H2O2Reagent
Soak sample 10min, take out post-drying, to remove sample surfaces organic remains；
(1.2) the 4H-SiC print removing after the organic remains of surface is reused HCl+H2O2Reagent soaks sample
10min, takes out post-drying, to remove ionic contamination.
Step 2：The low-doped epitaxial layer of epitaxial growth N-type, such as shown in Fig. 3 (b).
The n-type doping extension of chemical vapor deposition CVD method epitaxial growth N doping is utilized on SiC sample after cleaning
Layer.Its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and magazine source is
Liquid nitrogen, carrier gas is pure hydrogen, and obtaining nitrogen doped concentration is 1x 1015cm-3, thickness is 5 μm of the low-doped epitaxial layer of N-type.
Step 3：The highly doped epitaxial layer of epitaxial growth p-type, such as shown in Fig. 3 (c).
The low-doped epitaxial layer of epitaxial growth N-type utilize the p-type of chemical vapor deposition CVD epitaxial growth aluminum doping high
Doped epitaxial layer, its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is silane and propane,
Carrier gas is pure hydrogen, and impurity source is trimethyl aluminium, and obtaining aluminum doping content is 1x 1019cm-3, thickness is that 1 μm of p-type is highly doped
Epitaxial layer.
Step 4：Deposit Ohm contact electrode, such as shown in Fig. 3 (d).
(4.1) RCA standard cleaning is carried out to the SiC sample completing after the highly doped outer layer growth of p-type；
(4.2) print after cleaning is put on the microscope slide in electron beam evaporation deposition machine, adjustment microscope slide is to target
Distance be 50cm, and by reaction chamber pressure be evacuated to 5 × 10-4Pa, regulation line is 40mA, highly doped outer in the p-type of SiC sample
The surface deposition a layer thickness prolonging layer is the Ni metal level of 300nm；
(4.3) utilize electron-beam vapor deposition method, deposit, at the back side of the non-extension of substrate Si C, the Ni gold that a layer thickness is 300nm
Belong to layer；
At (4.4) 1100 DEG C, short annealing 3 minutes in nitrogen atmosphere.
Step 5：The Ni metal level of SiC extension one outgrowth carves structure graph window, such as shown in Fig. 3 (e).
(5.1) one layer of photoresist of spin coating on the Ni layer on surface of metal of SiC extension one outgrowth, according to two grooves of battery
Position be fabricated to reticle, with electron beam to photoresist expose, formed corrosion window；
(5.2) reactive ion technique is utilized to etch Ni metal level, reacting gas adopts oxygen, exposes the highly doped extension of p-type
Layer, obtains the etching window of p-type Ohm contact electrode and groove.
Step 6：Etching groove, such as shown in Fig. 3 (f).
Using inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial layer of the p-type that etching groove window exposes
Carve depth and be 6.5 μm, width is 5 μm, and spacing is 12 μm of two grooves.
Step 7：Place αsource, such as shown in Fig. 3 (g).
Method using depositing or smear, places αsource Am in each trench241, obtain 3D formula PIN structural alpha irradiation
Battery.
Embodiment 2, preparing αsource is Am241, there is the 3D formula PIN structural alpha irradiation battery of five grooves.
Step one:Cleaning 4H-SiC print, to remove surface contaminant, such as Fig. 3 (a).
This step is identical with the step 1 of embodiment 1.
Step 2：The low-doped epitaxial layer of epitaxial growth N-type, such as Fig. 3 (b).
Utilize the N-type of chemical vapor deposition CVD method epitaxial growth N doping low-doped outer in SiC sample after cleaning
Prolong layer.Its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is
Pure hydrogen, magazine source is liquid nitrogen, and completing nitrogen doped concentration is 1.5x 1015cm-3, thickness is 8 μm of the low-doped extension of N-type
The growth of layer.
Step 3：The highly doped epitaxial layer of epitaxial growth p-type, such as shown in Fig. 3 (c).
Using the p-type of chemical vapor deposition CVD epitaxial growth Al-doping on the low-doped epitaxial layer of N-type of growth
Highly doped epitaxial layer, its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is silane and third
Alkane, carrier gas is pure hydrogen, and impurity source is trimethyl aluminium, and completing aluminum doping content is 3x 1019cm-3, thickness is 1.5 μm of p-type
The growth of highly doped epitaxial layer.
Step 4：Deposit Ohm contact electrode, such as Fig. 3 (d).
This step is identical with the step 4 of embodiment one.
Step 5：Structure graph window is carved, such as Fig. 3 (e) on the Ni metal level of SiC extension one outgrowth.
(5.1) one layer of photoresist of spin coating on the Ni layer on surface of metal of SiC extension one outgrowth, according to five ditches of battery
The position of groove is fabricated to reticle, with electron beam, photoresist is exposed, and forms corrosion window；
(5.2) reactive ion technique is utilized to etch Ni metal level, reacting gas adopts oxygen, exposes the highly doped extension of p-type
Layer, obtains the etching window of p-type Ohm contact electrode and groove.
Step 6：Etching groove, such as Fig. 3 (f).
Using inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial layer of the p-type that etching groove window exposes
Carve depth and be 10 μm, width is 10 μm, and spacing is 20 μm of five grooves；
Step 7：Place αsource, such as Fig. 3 (g).
This step is identical with the step 7 of embodiment one.
Embodiment 3, preparing αsource is Pu238, there is the 3D formula PIN structural alpha irradiation battery of 10 grooves.
Step A:Cleaning 4H-SiC print, to remove surface contaminant, such as Fig. 3 (a).
This step is identical with the step 1 of embodiment 1.
Step B：Mixed using the N-type of chemical vapor deposition CVD method epitaxial growth N doping in SiC sample after cleaning
Miscellaneous epitaxial layer.Its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, carries
Gas is pure hydrogen, and magazine source is liquid nitrogen.Obtaining nitrogen doped concentration is 2x 1015cm-3, thickness is that 10 μm of N-type is low-doped
Epitaxial layer such as Fig. 3 (b).
Step C：Chemical vapor deposition CVD epitaxial growth aluminium ion is utilized on the low-doped epitaxial layer of epitaxial growth N-type
The highly doped epitaxial layer of p-type of doping, its process conditions is：Epitaxial temperature is 1570 DEG C, and pressure is 100mbar, and reacting gas is
Silane and propane, carrier gas is pure hydrogen, and impurity source is trimethyl aluminium, and obtaining aluminum doping content is 5x1019cm-3, thickness be 2 μm
P-type highly doped epitaxial layer such as Fig. 3 (c).
Step D：Deposit Ohm contact electrode, such as Fig. 3 (d).
This step is identical with the step 4 of embodiment one.
Step E：One layer of photoresist of spin coating on the Ni layer on surface of metal of SiC extension one outgrowth, according to 10 ditches of battery
The position of groove is fabricated to reticle, with electron beam, photoresist is exposed, and forms corrosion window；Then reactive ion technique is utilized to carve
Erosion Ni metal level, reacting gas adopts oxygen, exposes the highly doped epitaxial layer of p-type, obtain the quarter of p-type Ohm contact electrode and groove
Fenetre mouth such as Fig. 3 (e).
Step F：Using inductively coupled plasma ICP lithographic technique, the p-type exposed in etching groove window is highly doped outer
Prolong and depth is carved on layer for 12 μm, width is 14 μm, and spacing is 25 μm 10 groove such as Fig. 3 (f).
Step G：Method using depositing or smear, places αsource Pu in each trench238, obtain 3D formula PIN junction
Structure alpha irradiation battery such as Fig. 3 (g).
Claims (1)
1. a kind of preparation method of 3D formula PIN structural alpha irradiation battery, comprises the following steps：
1) clean：SiC sample is carried out, to remove surface contaminant；
2) grow the low-doped epitaxial layer of N-type：Using the SiC sample surface epitaxial growth after cleaning of chemical vapor deposition CVD
One layer of doping content is 1x1015～2x1015cm-3, thickness is 5～10 μm of the low-doped epitaxial layer of N-type；
3) the highly doped epitaxial layer of growing P-type：Using chemical vapor deposition CVD in N-type low-doped epi-layer surface epitaxial growth
One layer of doping content is 1x1019～5x1019cm-3, thickness is 1～2 μm of the highly doped epitaxial layer of p-type；
4) deposit Ohm contact electrode：Depositing a layer thickness in the highly doped epi-layer surface of p-type using electron-beam vapor deposition method is
The Ni metal level of 300nm, the mask as etching groove and p-type metal ohmic contact；Using electron-beam vapor deposition method in SiC substrate
The back side deposition thickness of non-extension is the Ni metal level of 300nm, as N-type Ohm contact electrode；In nitrogen atmosphere at 1100 DEG C
Short annealing 3 minutes；
5) litho pattern：Position according to nuclear battery groove is fabricated to reticle；One layer of the Ni layer on surface of metal spin coating in deposit
Photoresist, carries out electron beam exposure using reticle to photoresist, forms corrosion window；Ni metal level at corrosion window is entered
Row corrosion, exposes the highly doped epitaxial layer of p-type, obtains p-type Ohm contact electrode and trench etching window；
6) etching groove：Using inductively coupled plasma ICP lithographic technique, carve for placing αsource, depth is 6.5
～12 μm, width is 5～14 μm, and spacing is 12～25 μm of at least two grooves；
7) place αsource：Method using depositing or smear, places αsource in the trench, obtains 3D formula PIN structural α spoke
According to battery.
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| CN113990548B (en) * | 2021-10-09 | 2024-01-23 | 西安电子科技大学 | Groove Pin type beta irradiation battery with gate electrode surface field and preparation method |
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| CN101599309A (en) * | 2009-06-30 | 2009-12-09 | 西北工业大学 | SiC Schottky junction type Alpha radioisotope battery and preparation method thereof |
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