CN103730183A - Manufacturing method of silicon carbide schottky junction type nuclear battery including niobium-doped n-type epitaxial layer - Google Patents

Manufacturing method of silicon carbide schottky junction type nuclear battery including niobium-doped n-type epitaxial layer Download PDF

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CN103730183A
CN103730183A CN201310515692.9A CN201310515692A CN103730183A CN 103730183 A CN103730183 A CN 103730183A CN 201310515692 A CN201310515692 A CN 201310515692A CN 103730183 A CN103730183 A CN 103730183A
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epitaxial loayer
layer
schottky
silicon carbide
niobium
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梅欣
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LIYANG ZHEDA ACADEMIA RESEARCH SERVICE CENTER Co Ltd
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LIYANG ZHEDA ACADEMIA RESEARCH SERVICE CENTER Co Ltd
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Abstract

The invention discloses a manufacturing method of a silicon carbide schottky junction type nuclear battery including a niobium-doped n-type epitaxial layer. The battery sequentially comprises an n-type ohmic contact electrode 8, an n-type SiC substrate 7, an n-type SiC epitaxial layer 6, an SiO2 passivation layer 5, a schottky metal contact layer 4, a schottky contact electrode 3, a bonding layer 2 and a radioactive isotope source layer 1 from down to top, wherein the n-type SiC epitaxial layer 6 is formed by injecting 2000KeV-2500KeV energy for the initial n-type SiC epitaxial layer, injecting 5*1013-1*1015cm-2 niobium ions and then performing thermal annealing at the high temperature of 1450-1650 DEG C for 20-40 minutes, wherein the dosage concentration of the n-type SiC epitaxial layer is 1*1013-5*1014cm-3. By adopting the manufacturing method, the carrier concentration of the n-type epitaxial layer can be reduced, the depletion region width can be increased, the collection efficiency of produced electron hole pairs can be improved, and further the open-circuit voltage and energy conversion efficiency of a device can be improved.

Description

Comprise the manufacture method of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer
Technical field
The invention belongs to nuclear technology and microelectronics interleaving techniques field, relate in particular to a kind of manufacture method of silicon carbide Schottky junction type nuclear battery, it can directly be converted to electric energy by the nuclear energy of isotope radiation.
Technical background
Nineteen fifty-three, it is found that and utilize the isotope β particle producing that decays can in semiconductor, produce electron hole pair, and this phenomenon is called as β voltage effects.Nineteen fifty-seven, first people are used in power supply supply side by β voltage effects, and successfully experiment produces first radioisotope micro battery.Since 1989, GaN, GaP, AlGaAs, the materials such as polysilicon are utilized the material as β-Voltaic battery in succession.Along with the preparation of semiconductor material with wide forbidden band SiC and the progress of technology, 2006 start, and have in succession occurred the relevant report of the radioisotope micro battery based on SiC on both at home and abroad.
In Chinese patent literature CN101325093A, disclose a kind of Schottky junction type nuclear cell based on SiC, it comprises bonded layer, schottky metal layer, SiO from top to bottom successively 2passivation layer, the low-doped SiC epitaxial loayer of N-shaped, the highly doped SiC substrate of N-shaped, Ohm contact electrode.This schottky junction nuclear battery schottky contact layer covers whole cell area, incident particle arrives after device surface, capital is subject to stopping of schottky contact layer, only have part particle can enter device inside, and the particle that enters depletion region just can have contribution to the output power of battery, therefore, the nuclear battery projectile energy loss of this structure is large, and energy conversion efficiency is lower.
Summary of the invention
The object of the invention is to avoid above-mentioned the deficiencies in the prior art, a kind of method for making of the silicon carbide Schottky junction type nuclear battery that comprises niobium Doped n-type epitaxial loayer is proposed, the method can reduce the carrier concentration of N-shaped epitaxial loayer, increase width of depletion region, improve the collection rate of the electron hole pair producing, and then improve open-circuit voltage and the energy conversion efficiency of device.
For achieving the above object, the method for making of silicon carbide Schottky junction type nuclear battery provided by the invention, comprises the steps:
(1) on highly doped N-shaped SiC substrate, epitaxial growth thickness is 3um～5um, and nitrating concentration is 1 × 10 15～5 × 10 15cm -3initial N-shaped SiC epitaxial loayer;
(2) on initial N-shaped SiC epitaxial loayer, carrying out Implantation Energy is 2000KeV～2500KeV again, and implantation dosage is 5 × 10 13～1 × 10 15cm -2niobium ion inject, then thermal annealing 20～40 minutes under the high temperature of 1450 ℃～1650 ℃, and then to obtain doping content be 1 × 10 13～5 × 10 14cm -3n-shaped SiC epitaxial loayer;
(3) to doping content, be 1 × 10 13～5 × 10 14cm -3n-shaped SiC epitaxial loayer carry out dry-oxygen oxidation, form SiO 2passivation layer;
(4) use reactive ion etching method at the back-etching SiC of N-shaped SiC substrate layer, electron beam evaporation Ni/Cr/Au metal level, in nitrogen atmosphere, annealing forms Ohm contact electrode;
(5) at SiO 2the centre of passivation layer utilizes wet etching to go out Schottky contacts window, and on this window and the SiO of window periphery 2on passivation layer, the translucent high barrier schottky metal Ni of deposit or Pt or Au, peel off and form respectively schottky metal contact layer and Schottky contact electrode;
(6) on Schottky contact electrode, deposited by electron beam evaporation Cr/Au forms bonded layer;
(7) on schottky metal contact layer, plate radioactive isotope power supply Ni-63 layer, complete the making of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer.
The present invention compared with prior art tool has the following advantages: the silicon carbide Schottky junction type nuclear battery that the present invention makes, because N-shaped epitaxial loayer is to adopt nitrating epitaxial growth, then N-shaped epitaxial loayer being carried out to niobium ion injection again compensates the free carrier on epitaxial loayer energy level, therefore the charge carrier doping content of N-shaped epitaxial loayer is extremely low, increase width of depletion region, improve the collection rate of the electron hole pair producing, and then improve open-circuit voltage and the energy conversion efficiency of device;
Accompanying drawing explanation
Fig. 1 is the cross-sectional view of silicon carbide Schottky junction type nuclear battery of the present invention.
Embodiment
As shown in Figure 1, silicon carbide Schottky junction type nuclear battery of the present invention comprises N-shaped Ohm contact electrode 8, N-shaped SiC substrate 7, N-shaped SiC epitaxial loayer 6, SiO 2passivation layer 5, schottky metal contact layer 4, Schottky contact electrode 3, bonded layer 2 and radioactive isotope power supply layer 1, wherein the doping content of N-shaped SiC substrate 7 is 1 × 10 18～7 × 10 18cm -3, its back side is the N-shaped Ohm contact electrode 8 that is divided the Ni/Cr/Au alloy composition of 200nm/50nm/100nm by thickness, and front is that thickness is 3um～5um, and doping content is 1 × 10 13～5 × 10 14cm -3n-shaped SiC epitaxial loayer 6, this N-shaped SiC epitaxial loayer 6 is 2000KeV～2500KeV by Implantation Energy, dosage is 5 × 10 13～1 × 10 15cm -2niobium ion form.N-shaped SiC epitaxial loayer 6 tops, left and right are SiO 2passivation layer 5, is Schottky contacts metal level 4 and Schottky contact electrode 3 directly over N-shaped SiC epitaxial loayer 6, and the top, left and right of Schottky contact electrode 3 is bonded layer 2, is isotope source layer 1 directly over Schottky contacts metal level 4.
The method for making of nuclear battery of the present invention provides following three kinds of embodiment.
Embodiment 1
Step 1, extension N-shaped epitaxial loayer on the highly doped N-shaped substrate of SiC print.
Selecting doping content is 1 × 10 18cm -3highly doped N-shaped SiC substrate 7, after cleaning, on highly doped N-shaped SiC substrate, epitaxial growth thickness is 4um, the initial N-shaped epitaxial loayer of nitrogen ion doping, its doping content is 1 × 10 15cm -3, epitaxial temperature is 1570 ℃, and pressure is 100mbar, and reacting gas is silane and propane, and its flow is respectively 50sccm and 150sccm, and carrier gas is pure hydrogen, and impurity source is liquid nitrogen.
Step 2: be 1 × 10 to nitrating concentration 15cm -3initial N-shaped SiC epitaxial loayer carries out niobium ion injection.
(2.1) to nitrating concentration, be 1 × 10 15cm -3initial N-shaped SiC epitaxial loayer carry out niobium ion injection, its niobium ion injection condition is: the energy of Implantation is 2200KeV, implantation dosage is 5 × 10 13cm -2, to guarantee that the maximum concentration of niobium ion is greater than the doping content of the epitaxial loayer after nitrating;
(2.2) the N-shaped SiC epitaxial loayer after Implantation is carried out to high-temperature thermal annealing, make to inject ion redistribution, reduce lattice damage, and then to obtain doping content be 1 × 10 13cm -3low-doped N-shaped SiC epitaxial loayer 6, the condition of its high-temperature thermal annealing is: annealing temperature is 1450 ℃, annealing time is 40 minutes.
Step 3: be 1 × 10 in doping content 13cm -3on N-shaped SiC epitaxial loayer, form SiO 2passivation layer.
At 1100 ± 50 ℃ of temperature, N-shaped SiC epitaxial loayer 6 is carried out to the dry-oxygen oxidation of two hours, form SiO 2passivation layer 5.
Step 4: form Ohmic contact at substrate back.
(4.1) the SiC layer that is 0.5um by reactive ion etching method at the back-etching thickness of N-shaped SiC substrate 7;
(4.2) N-shaped SiC substrate 7 back side deposited by electron beam evaporation thickness after etching are respectively the Ni/Cr/Au of 200nm/50nm/200nm;
(4.3), at 1100 ± 50 ℃ of temperature, in nitrogen atmosphere, whole sample annealing is formed to Ohm contact electrode 8 for two minutes.
Step 5: deposit schottky metal contact layer and Schottky contact electrode.
(5.1) the HF acid corrosion that employing concentration is 5% 10 seconds, at SiO 2the centre position of passivation layer 3 erodes away Schottky contacts window;
(5.2) at the SiO of the window eroding away and window periphery 2the Ni that on passivation layer, d.c. sputtering deposition thickness is 5nm;
(5.3) by ultrasound wave, peel off respectively and form schottky metal contact layer 4 at described window, at the SiO of described window periphery 2on passivation layer, form Schottky contact electrode 3;
Step 6: make bonded layer on Schottky contact electrode.
On Schottky contact electrode 3, first deposited by electron beam evaporation thickness is respectively 10nm/200nm Cr/Au, then is peeled off and formed bonded layer 2 by ultrasound wave.
Step 7: power on and plate radioactive isotope power supply Ni-63 layer 1 at schottky metal contact layer 4.
Embodiment 2
Step 1: extension N-shaped epitaxial loayer on the highly doped N-shaped substrate of SiC print.
Selecting doping content is 5 × 10 18cm -3highly doped N-shaped SiC substrate 7, after cleaning, on highly doped N-shaped SiC substrate, epitaxial growth thickness is 3um, the initial N-shaped epitaxial loayer of nitrogen ion doping, its doping content is 5 × 10 15cm -3, epitaxial temperature is 1570 ℃, pressure 100mbar, and reacting gas is silane and propane, and its flow is respectively 50sccm and 150sccm, and carrier gas is pure hydrogen, and impurity source is liquid nitrogen.
Step 2: be 5 × 10 to nitrating concentration 15cm -3initial N-shaped SiC epitaxial loayer carries out niobium ion injection.
(2.1) to nitrating concentration, be 5 × 10 15cm -3initial N-shaped SiC epitaxial loayer carry out niobium ion injection, its niobium ion injection condition is: the energy of Implantation is 2000KeV, implantation dosage is 1 × 10 15cm -2, to guarantee that the maximum concentration of niobium ion is greater than the doping content of the epitaxial loayer after nitrating;
(2.2) the N-shaped SiC epitaxial loayer after Implantation is carried out to high-temperature thermal annealing, make to inject ion redistribution, reduce lattice damage, and then to obtain doping content be 5 × 10 14cm -3low-doped N-shaped SiC epitaxial loayer 6, the condition of its high-temperature thermal annealing is: annealing temperature is 1550 ℃, annealing time is 40 minutes.
Step 3: be 5 × 10 in assorted concentration 14cm -3on N-shaped SiC epitaxial loayer, form SiO 2passivation layer.
At 1100 ± 50 ℃ of temperature, N-shaped SiC epitaxial loayer 6 is carried out to the dry-oxygen oxidation of two hours, form SiO 2passivation layer 5.
The 4th step: form Ohmic contact at substrate back.
(4.1) the SiC layer that is 0.5um by reactive ion etching method at the back-etching thickness of N-shaped SiC substrate 7;
(4.2) N-shaped SiC substrate 7 back side deposited by electron beam evaporation thickness after etching are respectively the Ni/Cr/Au of 200nm/50nm/200nm;
(4.3), at 1100 ± 50 ℃ of temperature, in nitrogen atmosphere, whole sample annealing is formed to Ohm contact electrode 8 for two minutes.
The 5th step: deposit schottky metal contact layer and Schottky contact electrode.
(5.1) the HF acid corrosion that employing concentration is 5% 10 seconds, at SiO 2the centre position of passivation layer 3 erodes away Schottky contacts window;
(5.2) at the SiO of the window eroding away and window periphery 2the Pt that on passivation layer, d.c. sputtering deposition thickness is 10nm;
(5.3) by ultrasound wave, peel off respectively and form schottky metal contact layer 4 at described window, at the SiO of described window periphery 2on passivation layer, form Schottky contact electrode 3;
The 6th step: make bonded layer on Schottky contact electrode.
On Schottky contact electrode 3, first deposited by electron beam evaporation thickness is respectively 10nm/200nm Cr/Au, then is peeled off and formed bonded layer 2 by ultrasound wave.
The 7th step: radioactive isotope power supply Ni-63 layer 1 in electroless plating on schottky metal contact layer 4.
Embodiment 3
Steps A: extension N-shaped epitaxial loayer on the highly doped N-shaped substrate of SiC print.
Selecting doping content is 7 × 10 18cm -3highly doped N-shaped SiC substrate 7, after cleaning, on highly doped N-shaped SiC substrate, epitaxial growth thickness is 5um, the initial N-shaped epitaxial loayer of nitrogen ion doping, its doping content is 2 × 10 15cm -3, epitaxial temperature is 1570 ℃, pressure 100mbar, and reacting gas is silane and propane, and its flow is respectively 50sccm and 150sccm, and carrier gas is pure hydrogen, and impurity source is liquid nitrogen.
Step B: be 2 × 10 to nitrating concentration 15cm -3initial N-shaped SiC epitaxial loayer carries out niobium ion injection.
(B1) to nitrating concentration, be 2 × 10 15cm -3initial N-shaped SiC epitaxial loayer carry out niobium ion injection, its niobium ion injection condition is: the energy of Implantation is 2500KeV, implantation dosage is 1 × 10 14cm -2, to guarantee that the maximum concentration of niobium ion is greater than the doping content of the epitaxial loayer after nitrating;
(B2) the N-shaped SiC epitaxial loayer after Implantation is carried out to high-temperature thermal annealing, make to inject ion redistribution, reduce lattice damage, and then to obtain doping content be 5 × 10 13cm -3low-doped N-shaped SiC epitaxial loayer 6, the condition of its high-temperature thermal annealing is: annealing temperature is 1650 ℃, annealing time is 20 minutes.
Step C: be 5 × 10 in assorted concentration 13cm -3on N-shaped SiC epitaxial loayer, form SiO 2passivation layer.
At 1100 ± 50 ℃ of temperature, N-shaped SiC epitaxial loayer 6 is carried out to the dry-oxygen oxidation of two hours, form SiO 2passivation layer 5.
D step: form Ohmic contact at substrate back.
(4.1) the SiC layer that is 0.5um by reactive ion etching method at the back-etching thickness of N-shaped SiC substrate 7;
(4.2) N-shaped SiC substrate 6 back side deposited by electron beam evaporation thickness after etching are respectively the Ni/Cr/Au of 200nm/50nm/200nm;
(4.3), at 1100 ± 50 ℃ of temperature, in nitrogen atmosphere, whole sample annealing is formed to Ohm contact electrode 8 for two minutes.
E step: deposit schottky metal contact layer and Schottky contact electrode.
(5.1) the HF acid corrosion that employing concentration is 5% 10 seconds, at SiO 2the centre position of passivation layer 3 erodes away Schottky contacts window;
(5.2) at the SiO of the window eroding away and window periphery 2the Au that on passivation layer, d.c. sputtering deposition thickness is 20nm;
(5.3) by ultrasound wave, peel off respectively and form schottky metal contact layer 4 at described window, at the SiO of described window periphery 2on passivation layer, form Schottky contact electrode 3;
F step: make bonded layer on Schottky contact electrode.
On Schottky contact electrode 3, first deposited by electron beam evaporation thickness is respectively 10nm/200nm Cr/Au, then is peeled off and formed bonded layer 2 by ultrasound wave.
G step: radioactive isotope power supply Ni-63 layer 1 in molecular plating on schottky metal contact layer 4.
From the above description of this invention, can obviously learn, the present invention can change with many forms, and energy and dosage that particularly niobium ion injects need carrier concentration according to actual needs to determine.And these variations can not be considered to exceed technological thought of the present invention and scope.And, to those skilled in the art, within these apparent variant are all included in the scope of the claims in the present invention book.

Claims (6)

1. a manufacture method that comprises the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer, comprises the steps:
(1) on highly doped N-shaped SiC substrate, epitaxial growth thickness is 3um～5um, and nitrating concentration is 1 × 10 15～5 × 10 15cm -3initial N-shaped SiC epitaxial loayer;
(2) on initial N-shaped SiC epitaxial loayer, carrying out Implantation Energy is 2000KeV～2500KeV again, and implantation dosage is 5 × 10 13～1 × 10 15cm -2niobium ion inject, then thermal annealing 20～40 minutes under the high temperature of 1450 ℃～1650 ℃, and then to obtain doping content be 1 × 10 13～5 × 10 14cm -3n-shaped SiC epitaxial loayer;
(3) to doping content, be 1 × 10 13～5 × 10 14cm -3n-shaped SiC epitaxial loayer carry out dry-oxygen oxidation, form SiO 2passivation layer;
(4) use reactive ion etching method at the back-etching SiC of N-shaped SiC substrate layer, electron beam evaporation Ni/Cr/Au metal level, in nitrogen atmosphere, annealing forms Ohm contact electrode;
(5) at SiO 2the centre of passivation layer utilizes wet etching to go out Schottky contacts window, and on this window and the SiO of window periphery 2on passivation layer, the translucent high barrier schottky metal Ni of deposit or Pt or Au, peel off and form respectively schottky metal contact layer and Schottky contact electrode;
(6) on Schottky contact electrode, deposited by electron beam evaporation Cr/Au forms bonded layer;
(7) on schottky metal contact layer, plate radioactive isotope power supply Ni-63 layer, complete the making of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer.
2. the silicon carbide Schottky junction type nuclear battery that comprises niobium Doped n-type epitaxial loayer according to claim 1, is characterized in that, the maximum concentration that injects niobium ion is greater than the doping content of the epitaxial loayer after nitrating.
3. the method for making of the silicon carbide Schottky junction type nuclear battery that comprises niobium Doped n-type epitaxial loayer according to claim 1, it is characterized in that, dry-oxygen oxidation in described step (3), is to be 1100 ± 50 ℃ of temperature in process conditions, under the condition of two hours time, carries out.
4. the method for making of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer according to claim 1, is characterized in that, the electron beam evaporation Ni/Cr/Au metal level that step (4) is described, and its thickness is respectively 200nm/50nm/200nm.
5. the method for making of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer according to claim 1, is characterized in that, the thickness of the described translucent high barrier schottky metal contact layer of step (5) is less than or equal to 20nm.
6. the method for making of the silicon carbide Schottky junction type nuclear battery of niobium Doped n-type epitaxial loayer according to claim 1, it is characterized in that, isotope source described in step (8) is to be plated on Schottky contact electrode by plating or electroless plating or molecular plating.
CN201310515692.9A 2013-10-26 2013-10-26 Manufacturing method of silicon carbide schottky junction type nuclear battery including niobium-doped n-type epitaxial layer Pending CN103730183A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102254581A (en) * 2011-06-30 2011-11-23 西安电子科技大学 SiC ring electrode PIN-type nuclear battery
CN102509569A (en) * 2011-10-19 2012-06-20 西安电子科技大学 Silicon carbide Schottky junction type nuclear cell with vanadium-doped I layer and production method of silicon carbide Schottky junction type nuclear cell
CN103021492A (en) * 2012-12-27 2013-04-03 长安大学 Silicon carbide transverse-pin penny-sized nuclear battery and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102254581A (en) * 2011-06-30 2011-11-23 西安电子科技大学 SiC ring electrode PIN-type nuclear battery
CN102509569A (en) * 2011-10-19 2012-06-20 西安电子科技大学 Silicon carbide Schottky junction type nuclear cell with vanadium-doped I layer and production method of silicon carbide Schottky junction type nuclear cell
CN103021492A (en) * 2012-12-27 2013-04-03 长安大学 Silicon carbide transverse-pin penny-sized nuclear battery and manufacturing method thereof

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Application publication date: 20140416