CN104064241A - Series connection type PIN structure beta irradiation battery and preparation method thereof - Google Patents

Series connection type PIN structure beta irradiation battery and preparation method thereof Download PDF

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Publication number
CN104064241A
CN104064241A CN201410299990.3A CN201410299990A CN104064241A CN 104064241 A CN104064241 A CN 104064241A CN 201410299990 A CN201410299990 A CN 201410299990A CN 104064241 A CN104064241 A CN 104064241A
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epitaxial loayer
highly doped
doped epitaxial
ray
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郭辉
黄海栗
宋庆文
王悦湖
张玉明
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Xidian University
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Xidian University
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Abstract

The invention discloses a series connection type PIN structure beta irradiation battery and a preparation method thereof. A silicon carbide PIN type beta irradiation battery fabricated in the prior art has problems of low energy conversion efficiency and limited output voltage, and the invention is mainly used to solve the problems. The series connection type PIN structure beta irradiation battery of the invention is composed of an upper PIN junction and a lower PIN junction which are serially connected. The upper PIN junction comprises an N-type highly-doped epitaxial layer, a P-type lightly-doped epitaxial layer, a P-type highly-doped substrate, and a P-type ohmic contact electrode. The lower PIN junction comprises an N-type ohmic contact electrode, an N-type highly-doped substrate, an N-type lightly-doped epitaxial layer, and a P-type highly-doped epitaxial layer. Each PIN junction includes a plurality of trenches. The highly-doped epitaxial layers of the two PIN junctions are in contact with each other through a metal transition layer. The upper and lower trenches are in mirror symmetry and communicated to each other. A beta radiation source is placed into each trench. According to the invention, advantages of large radiation source and semiconductor contact area, high nuclear raw material utilization rate and large battery output voltage can be realized, and the battery can be used to supply power to a small circuit in a lasting manner or supply power in occasions, such as polar regions, desert, etc.

Description

Tandem PIN structure β irradiation battery and preparation method thereof
Technical field
The invention belongs to microelectronic, relate to semiconductor device structure and preparation method thereof, specifically a kind of silicon carbide-based tandem PIN structure β irradiation battery and preparation method thereof, can be used for the nuclear energy of isotope radiation to be directly converted to electric energy.
Technical background
Nineteen fifty-three found by Rappaport research, and beta (β-Particle) radial energy that utilizes isotope to decay to produce produces electron-hole pair in semiconductor, and this phenomenon is called as β-Voltaic Effect.Nineteen fifty-seven, first Elgin-Kidde is used in power supply supply side by β-Voltaic Effect, successfully produces first radioisotope micro battery β-Voltaic Battery.Because radiator beta-ray is less than αsource to the damage of human body, obtain wider application at medical domain, as, pacemaker.Since 1989, the materials such as GaN, GaP, AlGaAs, polysilicon are utilized the material as β-Voltaic battery in succession.From 2006, along with the progress of semiconductor material with wide forbidden band SiC preparation and technology, there is the relevant report of the radioisotope micro battery based on SiC.
The Schottky junction type β irradiation battery based on SiC being proposed by the people such as Zhang Lin, Guo Hui is disclosed in Chinese patent CN 101325093A.In this schottky junction β irradiation 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 β irradiation battery projectile energy loss of this structure is large, and energy conversion efficiency is lower.
Document " Demonstration of a tadiation resistant; hight efficiency SiC betavoltaic " has been introduced the C.J.Eiting by New Mexico Qynergy Corporation, V.Krishnamoorthy and S.Rodgers, the people such as T.George have proposed silit p-i-n eliminant nuclear battery jointly, as shown in Figure 1.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 4 of P type, P type SiC layer 3, intrinsic i layer 2, the highly doped SiC substrate 1 of N-shaped and N-type Ohm contact electrode 5.In this structure, only have the raw charge carrier of irradiation in depletion layer and in a near minority diffusion length to be collected.And, for avoiding Ohm contact electrode to stop incident ion, P type Ohmic electrode is made in to a corner of device, make from P type Ohmic electrode the raw charge carrier of the irradiation away from transport process by compound, reduce energy transformation ratio, reduced the output current of battery.
Meanwhile, theoretical analysis points out that the output voltage of β irradiation battery can not be greater than the energy gap of the semiconductor material that β irradiation battery uses.Thereby, when how effectively improving the output voltage of β irradiation battery under precondition, also become an important research topic.
Summary of the invention
The object of the invention is to the deficiency for above-mentioned prior art, propose a kind of tandem PIN structure β irradiation battery, to strengthen the effective rate of utilization of radiator beta-ray, improve output current and the output voltage of battery.
The technical thought that realizes the object of the invention is: by radiator beta-ray is wrapped in to inside battery completely, and the barrier effect of the high energy β particle that elimination metal electrode gives off radiator beta-ray, the utilization factor of raising radiator beta-ray; Tie the structure being in series by two PIN, improve output voltage.
Technical thought of the present invention is achieved in that
One, tandem PIN structure β irradiation battery of the present invention, comprising: PIN unit and radiator beta-ray, is characterized in that: described PIN unit, adopts upper and lower two PIN knot in series; Upper PIN knot be followed successively by from bottom to top the highly doped epitaxial loayer 4 of N-type, the low-doped extension of P type layer by layer 3, the highly doped substrate 2 of P type, P type Ohm contact electrode 1, lower PIN knot is followed successively by N-type Ohm contact electrode 9, the highly doped substrate 8 of N-type, the low-doped epitaxial loayer 7 of N-type, the highly doped epitaxial loayer 6 of P type from bottom to top;
In described each PIN knot, be equipped with n groove 10, wherein n >=2;
Between the highly doped epitaxial loayer 4 of N-type in described upper PIN knot and the highly doped epitaxial loayer 6 of P type in lower PIN knot, be connected by transition metal layer 5, make groove in upper and lower PIN knot form Mirror Symmetry, the integrative-structure mutually connecting, all fills up radiator beta-ray 11 in each groove.
As preferably, it is the promethium that 63 nickel or relative atomic mass are 147 that radiator beta-ray 11 adopts relative atomic mass, i.e. Ni 63or Pm 147.
As preferably, the highly doped substrate 2 of described battery P type, the low-doped epitaxial loayer 3 of P type, the highly doped epitaxial loayer 4 of N-type, the highly doped epitaxial loayer 6 of P type, the low-doped epitaxial loayer 7 of N-type and the highly doped substrate 8 of N-type are 4H-SiC material, to improve serviceable life and the open-circuit voltage of battery.
As preferably, the width L that described radiator beta-ray is placed groove 10 meets L≤2g, and wherein, g is the average incident degree of depth of the high energy β particle that discharges of radiator beta-ray 11 in radiator beta-ray, is Ni for radiator beta-ray 63, its value is: g=6 μ m is Pm for radiator beta-ray 147, its value is: g=16 μ m.
As preferably, the degree of depth h that described radiator beta-ray is placed groove 10 meets m<h<m+r, wherein, and for upper PIN knot, m is the gross thickness of the highly doped epitaxial loayer 4 of N-type and its Ohm contact electrode, and r is the thickness of the low-doped epitaxial loayer 3 of P type; For lower PIN knot, m is the gross thickness of the highly doped epitaxial loayer 6 of P type and its Ohm contact electrode, and r is the thickness of the low-doped epitaxial loayer 7 of N-type.
As preferably, the spacing d of described adjacent two grooves 10 meets d>=i, and wherein, i is the average incident degree of depth of the high energy β particle that discharges of radiator beta-ray 11 in 4H-SiC, is Ni for radiator beta-ray 63, its value is: i=10 μ m; Be Pm for radiator beta-ray 147, its value is: i=15 μ m.
As preferably, described transition metal layer 5 is selected Al/Ti/Ni alloy, and its thickness is Al=250nm, Ti=50nm, Ni=200nm, metal A l contacts with the highly doped epitaxial loayer 6 of P type, metal Ni contacts with the highly doped epitaxial loayer 4 of N-type, and metal Ti layer is between Al layer and Ni layer.
As preferably, described P type Ohm contact electrode 1 all adopts metal Ni with N-type Ohm contact electrode 9, and the thickness of Ni metal level is 300～400nm.
Two, preparation method of the present invention comprises the following steps:
(1) PIN knot in making:
1a) selecting concentration is lx10 18cm -3p type SiC substrate, this P type SiC substrate is cleaned, to remove surface contaminant;
1b) the low-doped epitaxial loayer of growing P-type: utilizing the P type SiC substrate surface epitaxial growth one deck doping content of chemical vapor deposition CVD method after cleaning is 1x10 15～2x10 15cm -3, thickness is the low-doped epitaxial loayer of P type of 5～10 μ m;
1c) the highly doped epitaxial loayer of growth N-type: utilizing chemical vapor deposition CVD method is 1x10 in the low-doped epi-layer surface epitaxial growth of P type one deck doping content 19～5x10 19cm -3, thickness is the highly doped epitaxial loayer of the N-type of 0.2～0.8 μ m;
1d) deposit contact electrode: utilize electron-beam vapor deposition method deposit Ni/Ti metal level in the highly doped epi-layer surface of N-type, as mask and the N-type epitaxial loayer metal ohmic contact of etching groove; Utilize electron-beam vapor deposition method at the not back side deposited metal Ni of extension of P type SiC substrate, as P type Ohm contact electrode;
1e) litho pattern: be made into trench lithography version according to the position of nuclear battery groove, at Ti metal surface spin coating one deck photoresist of deposit, utilize trench lithography version to carry out electron beam exposure to photoresist, form etching window; Ti, Ni metal level to etching window place corrode, and expose the highly doped SiC epitaxial loayer of N-type, obtain N-type epitaxial loayer Ohm contact electrode and etching groove window;
1f) etching groove: utilize inductively coupled plasma ICP lithographic technique, on the highly doped SiC epitaxial loayer of the N-type of exposing, carving the degree of depth is 4～8 μ m, width is 5～14 μ m, and spacing is n the groove of 12～25 μ m, and removes the photoresist on all groove external metallization Ti surface;
1g) place radiator beta-ray: the method that adopts deposit or smear, in each groove, place radiator beta-ray, obtain being with fluted upper PIN knot;
(2) make lower PIN knot:
2a) selecting concentration is lx10 18cm -3n-type SiC substrate, this N-type SiC substrate is cleaned, to remove surface contaminant;
2b) the low-doped epitaxial loayer of growth N-type: utilizing the N-type SiC substrate surface epitaxial growth one deck doping content of chemical vapor deposition CVD method after cleaning is 1x10 15～2x10 15cm -3, thickness is the low-doped epitaxial loayer of the N-type of 5～10 μ m;
2c) the highly doped epitaxial loayer of growing P-type: utilizing chemical vapor deposition CVD method is 1x10 in the low-doped epi-layer surface epitaxial growth of N-type one deck doping content 19～5x10 19cm -3, thickness is the highly doped epitaxial loayer of P type of 0.2～0.8 μ m;
2d) deposit contact electrode: utilize electron-beam vapor deposition method deposit Al metal level in the highly doped epi-layer surface of P type, as mask and the P type epitaxial loayer metal ohmic contact of etching groove; Utilize electron-beam vapor deposition method at the not back side deposit Ni metal level of extension of SiC substrate, as N-type Ohm contact electrode;
2e) litho pattern: at the Al of deposit layer on surface of metal spin coating one deck photoresist, the trench lithography version in utilization in PIN knot technique is carried out electron beam exposure to photoresist, forms etching window; Al metal level to etching window place carries out etching, exposes the highly doped SiC epitaxial loayer of P type, obtains P type epitaxial loayer Ohm contact electrode and etching groove window;
2f) etching groove: utilize inductively coupled plasma ICP lithographic technique, on the highly doped SiC epitaxial loayer of the P type exposing, carving the degree of depth is 4～8 μ m, width is 5～14 μ m, and spacing is n the groove of 12～25 μ m, and removes the photoresist of the outside Al layer on surface of metal of all grooves;
2g) place radiator beta-ray: the method that adopts deposit or smear, in each groove, place radiator beta-ray, obtain being with fluted lower PIN knot;
(3) utilize bonding method that the N-type epitaxial loayer Ohm contact electrode in the P type epitaxial loayer Ohm contact electrode in lower PIN knot and upper PIN knot is pressed together, make the groove in upper and lower PIN knot form Mirror Symmetry, the mutual integrative-structure connecting, thereby complete the making of tandem PIN structure β irradiation battery.
Compared with prior art, tool has the following advantages in the present invention:
1. the present invention, due to by two PIN knot tandem compounds, has improved the output voltage of battery;
2. the present invention is due to radiator beta-ray is placed in to groove, make the high energy β particle of radiator beta-ray generation without passing P type or the highly doped epitaxial loayer of N-type and metal electrode thereof, and directly inject the space charge region of PIN knot, reduce the energy loss of high energy β particle, thereby improved the output current of collection of energy rate and battery;
3. the present invention, because groove width is not more than the twice of high energy β particle average incident degree of depth in radiator beta-ray material, has significantly reduced the energy attenuation of high energy β particle in radiator beta-ray inside, has further improved the output current of collection of energy rate and battery.
4. the present invention is because the backing material 4H-SiC adopting is larger than traditional material Si energy gap, and radiation-resisting performance is better, can reduce the damage of high energy β particle to device, improves the operating voltage of battery, extends the serviceable life of battery simultaneously.
Brief description of the drawings
Fig. 1 is the schematic cross-section of existing PIN nuclear battery;
Fig. 2 is the schematic cross-section of tandem PIN structure β irradiation battery of the present invention;
Fig. 3 is the process flow diagram that the present invention makes tandem PIN structure β irradiation battery;
Fig. 4 is the schematic flow sheet that the present invention makes PIN knot on tandem PIN structure β irradiation battery;
Fig. 5 is the schematic flow sheet that the present invention makes PIN knot under tandem PIN structure β irradiation battery.
Embodiment
With reference to Fig. 2, tandem PIN structure β irradiation battery of the present invention, comprising: PIN unit and radiator beta-ray, and described PIN unit, adopts upper and lower two PIN knot in series, wherein:
Upper PIN knot, comprises P type Ohm contact electrode 1, the highly doped substrate 2 of P type, the low-doped epitaxial loayer 3 of P type, the highly doped epitaxial loayer 4 of N-type.Wherein: the thickness of the highly doped epitaxial loayer 4 of N-type is 0.2～0.8 μ m; The thickness of the low-doped epitaxial loayer 3 of P type is 5～10 μ m, and it is positioned at the top of the highly doped epitaxial loayer 4 of N-type; The highly doped substrate 2 of P type is concentration lx10 18cm -3p type SiC substrate, it is positioned at the low-doped epitaxial loayer of P type 3 tops; It is the Ni metal of 300～400nm that P type Ohm contact electrode 1 adopts thickness, and it is positioned at the top of the highly doped substrate 2 of P type.
Lower PIN knot, comprises the highly doped epitaxial loayer 6 of P type, the low-doped epitaxial loayer 7 of N-type, the highly doped substrate 8 of N-type, N-type Ohm contact electrode 9.Wherein: it is that 300～400nm metal Ni is as contact electrode that N-type Ohm contact electrode 9 adopts thickness; The highly doped substrate 8 of N-type is concentration lx10 18cm -3n-type SiC substrate, it is positioned at the top of N-type Ohm contact electrode 9; The thickness of the low-doped epitaxial loayer 7 of N-type is 5～10 μ m, and it is positioned at the top of the highly doped substrate 8 of N-type; The thickness of the highly doped epitaxial loayer 6 of P type is 0.2～0.8 μ m, and it is positioned at the top of the low-doped epitaxial loayer 7 of N-type.
In each PIN knot, be equipped with n groove 10, wherein n>=2, the degree of depth h of groove 10 meets m<h<m+r, m is the highly doped epitaxial loayer 4 of N-type and the gross thickness of its Ohm contact electrode or the gross thickness of the highly doped epitaxial loayer 6 of P type and its Ohm contact electrode, and r is the thickness of the low-doped epitaxial loayer 3 of P type or the low-doped epitaxial loayer 7 of N-type; The width L of each groove 10 meets L≤2g, and wherein g is the average incident degree of depth of the high energy β particle that discharges of radiator beta-ray 11 in radiator beta-ray, is Ni for radiator beta-ray 63, its value is: g=6 μ m is Pm for radiator beta-ray 147, its value is: g=16 μ m; And the spacing d of adjacent two grooves 10 meets d>=i, i is the average incident degree of depth of the high energy β particle that discharges of radiator beta-ray 11 in 4H-SiC, is Ni for radiator beta-ray 63, its value is: i=10 μ m; Be Pm for radiator beta-ray 147, its value is: i=15 μ m; Radiator beta-ray 11 is placed in each groove 10, to produce high energy β particle.
The highly doped epitaxial loayer 4 of N-type of upper PIN knot is connected by transition metal layer 5 with the highly doped epitaxial loayer 6 of P type in lower PIN knot, thus a PIN unit of composition.The Ni metal level of the Al metal level that transition metal layer 5 is 250nm by thickness, the Ti metal level of 50nm, 200nm forms, wherein metal layer A l is positioned at the highly doped epitaxial loayer of P type 6 tops, metal Ti layer is positioned at above Al layer, and metal Ni contacts on metal level Ti and with the highly doped epitaxial loayer 4 of N-type.
Upper PIN knot is Mirror Symmetry with each groove 10 of lower PIN knot and distributes in PIN unit, connects together.
The highly doped substrate 2 of P type in above-mentioned PIN unit, the low-doped epitaxial loayer 3 of P type, the highly doped epitaxial loayer 4 of N-type, the highly doped epitaxial loayer 6 of P type, the low-doped epitaxial loayer 7 of N-type, the highly doped substrate 8 of N-type, be 4H-SiC material.
Under device duty, most of high energy β particle discharging from radiator beta-ray 11 is directly incident near the space charge region highly doped epitaxial loayer 4 of N-type and low-doped epitaxial loayer 3 intersections of P type, and the highly doped epitaxial loayer 6 of P type and near the space charge region of low-doped epitaxial loayer 7 intersections of N-type, and then excite charge carrier, finally form output current.
With reference to Fig. 3, the present invention makes the method for tandem PIN type β irradiation battery, provides following three embodiment:
Embodiment 1, preparing radiator beta-ray is Ni 63, there is the tandem PIN structure β irradiation battery of two grooves.
Step 1: PIN knot in making.
With reference to Fig. 4, being implemented as follows of this step:
(1a) clean the highly doped substrate of P type, to remove surface contaminant, as shown in Fig. 4 (a):
(1a.1) be lx10 by doping content 18cm -3highly doped P type 4H-SiC substrate at NH 4oH+H 2o 2in reagent, soak 10min, take out post-drying, to remove sample surfaces organic remains;
(1a.2) the P type 4H-SiC substrate of removing after surperficial organic remains is re-used to HCl+H 2o 2reagent soaks 10min, takes out post-drying, to remove ionic contamination.
(1b) the low-doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 4 (b):
On the highly doped substrate of P type after cleaning, utilize the low-doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping.Its process conditions are: epitaxial temperature is 1550 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and impurity source is trimethyl aluminium, and obtaining aluminium doping content is 1x10 15cm -3, thickness is the low-doped epitaxial loayer of P type of 5 μ m;
(1c) the highly doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 4 (c):
On the low-doped epitaxial loayer of P type of growth, utilize the highly doped epitaxial loayer of N-type of chemical vapor deposition CVD method epitaxial growth nitrogen doping, its process conditions are: epitaxial temperature is 1550 DEG C, pressure is 100mbar, reacting gas is silane and propane, carrier gas is pure hydrogen, impurity source is liquid nitrogen, and obtaining nitrogen doped concentration is 1x10 19cm -3, thickness is the highly doped epitaxial loayer of the N-type of 0.2 μ m, forms P type SiC print.
(1d) depositing metal contact electrode, as shown in Fig. 4 (d):
(1d.1) the P type SiC print completing after the highly doped outer layer growth of N-type is carried out to RCA standard cleaning;
(1d.2) print after cleaning is put on the microslide of electron beam evaporation deposition machine, adjusting microslide is 50cm to the distance of target, and reaction chamber pressure is evacuated to 5 × 10 -4pa, adjusting line is 40mA, at the surface Ni metal level that deposition thickness is 200nm successively of the highly doped epitaxial loayer of N-type of P type SiC print and the Ti metal level that thickness is 50nm;
(1d.3) utilize electron-beam vapor deposition method, at the above-mentioned P type SiC print Ni metal level that back side deposition thickness of extension is not 300nm.
(1e) on the Ti metal level of P type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 4 (e):
(1e.1) spin coating one deck photoresist on the Ti layer on surface of metal of P type SiC print extension one outgrowth, is made into trench lithography version according to the position of two grooves, photoresist is exposed with electron beam, forms etching window;
(1e.2) utilize reactive ion technique etching Ti, Ni metal level, until expose the highly doped epitaxial loayer of N-type in etching window, obtain N-type epitaxial loayer Ohm contact electrode and etching groove window.
(1f) etching groove, as shown in Fig. 4 (f):
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of N-type exposing at etching groove window, carving the degree of depth is 4 μ m, and width is 5 μ m, and spacing is two grooves of 12 μ m;
(1g) place radiator beta-ray, as shown in Fig. 4 (g):
The method that employing is smeared is placed radiator beta-ray Ni in each groove 63, obtain being with fluted upper PIN knot.
Step 2: make lower PIN knot.
With reference to Fig. 5, being implemented as follows of this step:
(2a) clean the highly doped substrate of N-type, to remove surface contaminant, the highly doped substrate of this N-type is 4H-SiC substrate, and doping content is lx10 18cm -3, as shown in Fig. 5 (a):
The enforcement of this step is identical with (1a) of step 1.
(2b) the low-doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 5 (b):
On the highly doped substrate of N-type after cleaning, utilize the low-doped epitaxial loayer of N-type of chemical vapor deposition CVD method epitaxial growth nitrogen doping.Its process conditions are: epitaxial temperature is 1550 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and impurity source is liquid nitrogen, and obtaining nitrogen doped concentration is 1x10 15cm -3, thickness is the low-doped epitaxial loayer of the N-type of 5 μ m.
(2c) the highly doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 5 (c):
On the low-doped epitaxial loayer of N-type of growth, utilize the highly doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping, its process conditions are: epitaxial temperature is 1550 DEG C, pressure is 100mbar, reacting gas is silane and propane, carrier gas is pure hydrogen, impurity source is trimethyl aluminium, and obtaining aluminium doping content is 1x10 19cm -3, thickness is the highly doped epitaxial loayer of P type of 0.2 μ m, obtains N-type SiC print.
(2d) depositing metal contact electrode, as shown in Fig. 5 (d):
(2d.1) the N-type SiC print completing after the highly doped outer layer growth of P type is carried out to RCA standard cleaning;
(2d.2) print after cleaning is put on the microslide of electron beam evaporation deposition machine, adjusting microslide is 50cm to the distance of target, and reaction chamber pressure is evacuated to 5 × 10 -4pa, adjusting line is 40mA, the Al metal level that is 250nm in surface deposition a layer thickness of the highly doped epitaxial loayer of P type of N-type SiC print;
(2d.3) utilize electron-beam vapor deposition method, at the above-mentioned N-type SiC print Ni metal level that back side deposition thickness of extension is not 300nm;
(2e) on the Al metal level of N-type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 5 (e):
(2e.1) spin coating one deck photoresist on the Al layer on surface of metal of N-type SiC print extension one outgrowth, the trench lithography version in utilization in PIN knot technique, exposes to photoresist with electron beam, forms etching window;
(2e.2) utilize reactive ion technique etching Al metal level, until expose the highly doped epitaxial loayer of P type in etching window, obtain P type epitaxial loayer Ohm contact electrode and etching groove window.
(2f) etching groove, as shown in Fig. 5 (f):
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of P type exposing at etching groove window, carving the degree of depth is 4 μ m, and width is 5 μ m, and spacing is two grooves of 12 μ m;
(2g) place radiator beta-ray, as shown in Fig. 5 (g).
The method that employing is smeared is placed radiator beta-ray Ni in each groove 63, obtain being with fluted lower PIN knot.
Step 3: utilize bonding method that the N-type epitaxial loayer Ohm contact electrode in the P type epitaxial loayer Ohm contact electrode in lower PIN knot and upper PIN knot is pressed together, make the groove in upper and lower PIN knot form Mirror Symmetry, the mutual integrative-structure connecting, thereby complete the making of tandem PIN structure β irradiation battery, as shown in Figure 2.
Embodiment 2, preparing radiator beta-ray is Ni 63, there is the tandem PIN structure β irradiation battery of 6 grooves.
Step 1: PIN knot in making.
With reference to Fig. 4, being implemented as follows of this step:
1) clean the highly doped substrate of P type, to remove surface contaminant, the highly doped substrate of this P type is 4H-SiC substrate, and doping content is lx10 18cm -3, as shown in Fig. 4 (a):
The enforcement of this step is identical with the step (1a) of embodiment mono-.
2) the low-doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 4 (b).
On the highly doped substrate of P type after cleaning, utilize the low-doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping.Be 1550 DEG C at epitaxial temperature, pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and under the process conditions that impurity source is trimethyl aluminium, obtaining aluminium doping content is 1.5x10 15cm -3, thickness is the low-doped epitaxial loayer of P type of 8 μ m.
3) the highly doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 4 (c).
On the low-doped epitaxial loayer of P type of growth, utilize the highly doped epitaxial loayer of N-type of chemical vapor deposition CVD method epitaxial growth nitrogen doping, it is 1550 DEG C at epitaxial temperature, pressure is 100mbar, reacting gas is silane and propane, carrier gas is pure hydrogen, impurity source is under the process conditions of liquid nitrogen, and obtaining nitrogen doped concentration is 3x10 19cm -3, thickness is the highly doped epitaxial loayer of the N-type of 0.5 μ m, obtains P type SiC print.
4) depositing metal contact electrode, as shown in Fig. 4 (d).
(4.1) enforcement of this step is identical with the step (1d.1) of embodiment mono-.
(4.2) enforcement of this step is identical with the step (1d.2) of embodiment mono-.
(4.3) utilize electron-beam vapor deposition method, at the above-mentioned P type SiC print Ni metal level that back side deposition thickness of extension is not 350nm.
5) on the Ti metal level of P type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 4 (e).
(5.1) spin coating one deck photoresist on the Ti layer on surface of metal of SiC extension one outgrowth, is made into trench lithography version according to the position of 6 grooves of battery, photoresist is exposed with electron beam, forms etching window;
(5.2) utilize reactive ion technique etching Ti, Ni metal level, reacting gas adopts oxygen, until expose the highly doped epitaxial loayer of N-type in etching window, obtains N-type epitaxial loayer Ohm contact electrode and etching groove window.
6) etching groove, as shown in Fig. 4 (f).
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of N-type exposing at etching groove window, carving the degree of depth is 6 μ m, and width is 10 μ m, and spacing is 6 grooves of 20 μ m.
7) place radiator beta-ray, as shown in Fig. 4 (g).
Adopt the method for deposit, in each groove, place radiator beta-ray Ni 63, obtain being with fluted upper PIN knot.
Step 2: make lower PIN knot.
With reference to Fig. 5, being implemented as follows of this step:
1) clean the highly doped substrate of N-type, to remove surface contaminant, the highly doped substrate of this N-type is 4H-SiC substrate, and doping content is lx10 18cm -3, as shown in Fig. 5 (a).
The enforcement of this step is identical with the step (1a) of embodiment 1.
2) the low-doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 5 (b).
On the highly doped substrate of N-type after cleaning, utilize the N-type doped epitaxial layer of chemical vapor deposition CVD method epitaxial growth nitrogen doping.Be 1550 DEG C at epitaxial temperature, pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and under the process conditions that impurity source is liquid nitrogen, obtaining nitrogen doped concentration is 1.5x10 15cm -3, thickness is the low-doped epitaxial loayer of the N-type of 8 μ m.
3) the highly doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 5 (c).
On the low-doped epitaxial loayer of N-type of growth, utilize the highly doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping.Be 1550 DEG C at epitaxial temperature, pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and under the process conditions that impurity source is trimethyl aluminium, obtaining aluminium doping content is 3x10 19cm -3, thickness is the highly doped epitaxial loayer of P type of 0.5 μ m, obtains N-type SiC print.
4) depositing metal contact electrode, as shown in Fig. 5 (d).
(4.1) enforcement of this step is identical with the step (2d.1) of embodiment mono-.
(4.2) enforcement of this step is identical with the step (2d.2) of embodiment mono-.
(4.3) utilize electron-beam vapor deposition method, at the above-mentioned N-type SiC print Ni metal level that back side deposition thickness of extension is not 350nm.
5) on the Al metal level of N-type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 5 (e).
(5.1) spin coating one deck photoresist on the Al layer on surface of metal of N-type SiC print extension one outgrowth, the trench lithography version in utilization in PIN knot technique, exposes to photoresist with electron beam, forms etching window;
(5.2) utilize reactive ion technique etching Al metal level, reacting gas adopts oxygen, until expose the highly doped epitaxial loayer of P type at etching groove window, obtains P type epitaxial loayer Ohm contact electrode and etching groove window.
6) etching groove, as shown in Fig. 5 (f).
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of P type exposing at etching groove window, carving the degree of depth is 6 μ m, and width is 10 μ m, and spacing is 6 grooves of 20 μ m;
7) place radiator beta-ray, as shown in Fig. 5 (g).
Adopt the method for deposit, in each groove, place radiator beta-ray Ni 63, obtain being with fluted lower PIN knot.
Step 3: utilize bonding method that the N-type epitaxial loayer Ohm contact electrode in the P type epitaxial loayer Ohm contact electrode in lower PIN knot and upper PIN knot is pressed together, make the groove in upper and lower PIN knot form Mirror Symmetry, the mutual integrative-structure connecting, thereby complete the making of tandem PIN structure β irradiation battery, as shown in Figure 2.
Embodiment 3, preparing radiator beta-ray is Pm 147, there is the tandem PIN structure β irradiation battery of 10 grooves.
Steps A: PIN knot in making.
With reference to Fig. 4, being implemented as follows of this step:
A1) clean the highly doped substrate of P type, to remove surface contaminant, the highly doped substrate of this P type is 4H-SiC substrate, and doping content is lx10 18cm -3, as shown in Fig. 4 (a):
The enforcement of this step is identical with the step (1a) of embodiment mono-.
A2) the low-doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 4 (b).
On the highly doped substrate of P type after cleaning, utilize the low-doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping.Its process conditions are: epitaxial temperature is 1550 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and impurity source is trimethyl aluminium, and obtaining aluminium doping content is 2x10 15cm -3, thickness is the low-doped epitaxial loayer of P type of 10 μ m.
A3) the highly doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 4 (c).
On the low-doped epitaxial loayer of P type of growth, utilize the highly doped epitaxial loayer of N-type of chemical vapor deposition CVD method epitaxial growth nitrogen doping, its process conditions are: epitaxial temperature is 1550 DEG C, pressure is 100mbar, reacting gas is silane and propane, carrier gas is pure hydrogen, impurity source is liquid nitrogen, and obtaining nitrogen doped concentration is 5x10 19cm -3, thickness is the highly doped epitaxial loayer of the N-type of 0.8 μ m, obtains P type SiC print.
A4) depositing metal contact electrode, as shown in Fig. 4 (d).
(A4.1) enforcement of this step is identical with the step (1d.1) of embodiment mono-.
(A4.2) enforcement of this step is identical with the step (1d.2) of embodiment mono-.
(A4.3) utilize electron-beam vapor deposition method, at the above-mentioned P type SiC print Ni metal level that back side deposition thickness of extension is not 400nm.
A5) on the Ti metal level of P type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 4 (e).
(A5.1) spin coating one deck photoresist on the Ti layer on surface of metal of P type SiC print extension one outgrowth, is made into reticle according to the position of 10 grooves of battery, photoresist is exposed with electron beam, forms etching window;
(A5.2) utilize reactive ion technique etching Ti, Ni metal level, reacting gas adopts oxygen, until expose the highly doped epitaxial loayer of N-type in etching window, obtains N-type epitaxial loayer Ohm contact electrode and etching groove window.
A6) etching groove, as shown in Fig. 4 (f).
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of N-type exposing at etching groove window, carving the degree of depth is 8 μ m, and width is 14 μ m, and spacing is 10 grooves of 25 μ m.
A7) place radiator beta-ray, as shown in Fig. 4 (g).
Adopt the method for deposit, in each groove, place radiator beta-ray Pm 147, obtain being with fluted upper PIN knot.
Step B: make lower PIN knot.
With reference to Fig. 5, being implemented as follows of this step:
B1) clean the highly doped substrate of N-type, to remove surface contaminant, the highly doped substrate of this N-type is 4H-SiC substrate, and doping content is lx10 18cm -3, as shown in Fig. 5 (a).
The enforcement of this step is identical with the step (1a) of embodiment 1.
B2) the low-doped epitaxial loayer of epitaxial growth N-type, as shown in Fig. 5 (b).
On the highly doped substrate of N-type after cleaning, utilize the N-type doped epitaxial layer of chemical vapor deposition CVD method epitaxial growth nitrogen doping.Its process conditions are: epitaxial temperature is 1550 DEG C, and pressure is 100mbar, and reacting gas is silane and propane, and carrier gas is pure hydrogen, and impurity source is liquid nitrogen, and obtaining nitrogen doped concentration is 2x10 15cm -3, thickness is the low-doped epitaxial loayer of the N-type of 10 μ m.
B3) the highly doped epitaxial loayer of epitaxial growth P type, as shown in Fig. 5 (c).
On the low-doped epitaxial loayer of N-type of growth, utilize the highly doped epitaxial loayer of P type of chemical vapor deposition CVD method epitaxial growth aluminium doping, its process conditions are: epitaxial temperature is 1550 DEG C, pressure is 100mbar, reacting gas is silane and propane, carrier gas is pure hydrogen, impurity source is trimethyl aluminium, and obtaining aluminium doping content is 5x10 19cm -3, thickness is the highly doped epitaxial loayer of P type of 0.8 μ m, obtains N-type SiC print.
B4) depositing metal contact electrode, as shown in Fig. 5 (d).
(B4.1) enforcement of this step is identical with the step (2d.1) of embodiment mono-.
(B4.2) enforcement of this step is identical with the step (2d.2) of embodiment mono-.
(B4.3) utilize electron-beam vapor deposition method, at the above-mentioned N-type SiC print Ni metal level that back side deposition thickness of extension is not 400nm.
B5) on the Al metal level of N-type SiC print extension one outgrowth, carve structure graph window, as shown in Fig. 5 (e).
(B5.1) spin coating one deck photoresist on the Al layer on surface of metal of N-type SiC print extension one outgrowth, the trench lithography version in utilization in PIN knot technique, exposes to photoresist with electron beam, forms etching window;
(B5.2) utilize reactive ion technique etching Al metal level, until expose the highly doped epitaxial loayer of P type in etching window, obtain P type epitaxial loayer Ohm contact electrode and etching groove window.
B6) etching groove, as shown in Fig. 5 (f).
Utilize inductively coupled plasma ICP lithographic technique, on the highly doped epitaxial loayer of P type exposing at etching groove window, carving the degree of depth is 8 μ m, and width is 14 μ m, and spacing is 10 grooves of 25 μ m.
B7) place radiator beta-ray, as shown in Fig. 5 (g).
Adopt the method for deposit, in each groove, place radiator beta-ray Pm 147, obtain being with fluted lower PIN knot.
Step C: utilize bonding method that the N-type epitaxial loayer Ohm contact electrode in the P type epitaxial loayer Ohm contact electrode in lower PIN knot and upper PIN knot is pressed together, make the groove in upper and lower PIN knot form Mirror Symmetry, the mutual integrative-structure connecting, thereby complete the making of tandem PIN structure β irradiation battery, as shown in Figure 2.

Claims (9)

1. a tandem PIN structure β irradiation battery, comprising: PIN unit and radiator beta-ray, is characterized in that:
Described PIN unit, adopts upper and lower two PIN knot in series; Upper PIN knot is followed successively by the highly doped epitaxial loayer of N-type (4), the low-doped epitaxial loayer of P type (3), the highly doped substrate of P type (2), P type Ohm contact electrode (1) from bottom to top, and lower PIN knot is followed successively by N-type Ohm contact electrode (9), the highly doped substrate of N-type (8), the low-doped epitaxial loayer of N-type (7), the highly doped epitaxial loayer of P type (6) from bottom to top;
In described each PIN knot, be equipped with n groove (10), wherein n >=2;
Between the highly doped epitaxial loayer of N-type (4) in described upper PIN knot and the highly doped epitaxial loayer of P type (6) in lower PIN knot, be connected by transition metal layer (5), make groove in upper and lower PIN knot form Mirror Symmetry, the integrative-structure mutually connecting, all fills up radiator beta-ray (11) in each groove.
2. battery according to claim 1, is characterized in that radiator beta-ray (11) to adopt relative atomic mass is 63 the promethium that nickel or relative atomic mass are 147, i.e. Ni 63or Pm 147.
3. battery according to claim 1, it is characterized in that, the highly doped substrate of P type (2), the low-doped epitaxial loayer of P type (3), the highly doped epitaxial loayer of N-type (4), the highly doped epitaxial loayer of P type (6), the low-doped epitaxial loayer of N-type (7) and the highly doped substrate of N-type (8) are 4H-SiC material, to improve serviceable life and the open-circuit voltage of battery.
4. battery according to claim 1, is characterized in that the width L of groove (10) meets L≤2g, and wherein, g is the average incident degree of depth of high energy β particle in radiator beta-ray that radiator beta-ray (11) discharges, and is Ni for radiator beta-ray 63, its value is: g=6 μ m is Pm for radiator beta-ray 147, its value is: g=16 μ m.
5. battery according to claim 1, the degree of depth h that it is characterized in that groove (10) meets m<h<m+r, wherein, for upper PIN knot, m is the gross thickness of the highly doped epitaxial loayer of N-type (4) and its Ohm contact electrode, and r is the thickness of the low-doped epitaxial loayer of P type (3); For lower PIN knot, m is the gross thickness of the highly doped epitaxial loayer of P type (6) and its Ohm contact electrode, and r is the thickness of the low-doped epitaxial loayer of N-type (7).
6. battery according to claim 1, the spacing d that it is characterized in that adjacent two grooves (10) meets d>=i, wherein, i is the average incident degree of depth of high energy β particle in 4H-SiC that radiator beta-ray (11) discharges, and is Ni for radiator beta-ray 63, its value is: i=10 μ m; Be Pm for radiator beta-ray 147, its value is: i=15 μ m.
7. battery according to claim 1, it is characterized in that transition metal layer (5) selects Al/Ti/Ni alloy, its thickness is Al=250nm, Ti=50nm, Ni=200nm, metal A l contacts with the highly doped epitaxial loayer of P type (6), and metal Ni contacts with the highly doped epitaxial loayer of N-type (4), and metal Ti layer is between Al layer and Ni layer.
8. battery according to claim 1, is characterized in that P type Ohm contact electrode (1) and N-type Ohm contact electrode (9) all adopt metal Ni, and the thickness of Ni metal level is 300～400nm.
9. a preparation method for tandem PIN structure β irradiation battery, comprises the following steps:
(1) PIN knot in making:
1a) selecting concentration is lx10 18cm -3p type SiC substrate, this P type SiC substrate is cleaned, to remove surface contaminant;
1b) the low-doped epitaxial loayer of growing P-type: utilizing the P type SiC substrate surface epitaxial growth one deck doping content of chemical vapor deposition CVD method after cleaning is 1x10 15～2x10 15cm -3, thickness is the low-doped epitaxial loayer of P type of 5～10 μ m;
1c) the highly doped epitaxial loayer of growth N-type: utilizing chemical vapor deposition CVD method is 1x10 in the low-doped epi-layer surface epitaxial growth of P type one deck doping content 19～5x10 19cm -3, thickness is the highly doped epitaxial loayer of the N-type of 0.2～0.8 μ m;
1d) deposit contact electrode: utilize electron-beam vapor deposition method deposit Ni/Ti metal level in the highly doped epi-layer surface of N-type, as mask and the N-type epitaxial loayer metal ohmic contact of etching groove; Utilize electron-beam vapor deposition method at the not back side deposited metal Ni of extension of P type SiC substrate, as P type Ohm contact electrode;
1e) litho pattern: be made into trench lithography version according to the position of nuclear battery groove, at Ti metal surface spin coating one deck photoresist of deposit, utilize trench lithography version to carry out electron beam exposure to photoresist, form etching window; Ti, Ni metal level to etching window place corrode, and expose the highly doped SiC epitaxial loayer of N-type, obtain N-type epitaxial loayer Ohm contact electrode and etching groove window;
1f) etching groove: utilize inductively coupled plasma ICP lithographic technique, on the highly doped SiC epitaxial loayer of the N-type of exposing, carving the degree of depth is 4～8 μ m, width is 5～14 μ m, and spacing is n the groove of 12～25 μ m, and removes the photoresist on all groove external metallization Ti surface;
1g) place radiator beta-ray: the method that adopts deposit or smear, in each groove, place radiator beta-ray, obtain being with fluted upper PIN knot;
(2) make lower PIN knot:
2a) selecting concentration is lx10 18cm -3n-type SiC substrate, this N-type SiC substrate is cleaned, to remove surface contaminant;
2b) the low-doped epitaxial loayer of growth N-type: utilizing the N-type SiC substrate surface epitaxial growth one deck doping content of chemical vapor deposition CVD method after cleaning is 1x10 15～2x10 15cm -3, thickness is the low-doped epitaxial loayer of the N-type of 5～10 μ m;
2c) the highly doped epitaxial loayer of growing P-type: utilizing chemical vapor deposition CVD method is 1x10 in the low-doped epi-layer surface epitaxial growth of N-type one deck doping content 19～5x10 19cm -3, thickness is the highly doped epitaxial loayer of P type of 0.2～0.8 μ m;
2d) deposit contact electrode: utilize electron-beam vapor deposition method deposit Al metal level in the highly doped epi-layer surface of P type, as mask and the P type epitaxial loayer metal ohmic contact of etching groove; Utilize electron-beam vapor deposition method at the not back side deposit Ni metal level of extension of SiC substrate, as N-type Ohm contact electrode;
2e) litho pattern: at the Al of deposit layer on surface of metal spin coating one deck photoresist, the trench lithography version in utilization in PIN knot technique is carried out electron beam exposure to photoresist, forms etching window; Al metal level to etching window place carries out etching, exposes the highly doped SiC epitaxial loayer of P type, obtains P type epitaxial loayer Ohm contact electrode and etching groove window;
2f) etching groove: utilize inductively coupled plasma ICP lithographic technique, on the highly doped SiC epitaxial loayer of the P type exposing, carving the degree of depth is 4～8 μ m, width is 5～14 μ m, and spacing is n the groove of 12～25 μ m, and removes the photoresist of the outside Al layer on surface of metal of all grooves;
2g) place radiator beta-ray: the method that adopts deposit or smear, in each groove, place radiator beta-ray, obtain being with fluted lower PIN knot;
(3) utilize bonding method that the N-type epitaxial loayer Ohm contact electrode in the P type epitaxial loayer Ohm contact electrode in lower PIN knot and upper PIN knot is pressed together, make the groove in upper and lower PIN knot form Mirror Symmetry, the mutual integrative-structure connecting, thereby complete the making of tandem PIN structure β irradiation battery.
CN201410299990.3A 2014-06-29 2014-06-29 Series connection type PIN structure beta irradiation battery and preparation method thereof Pending CN104064241A (en)

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