CN101872723B - Germanium tunnelling diode and preparation method thereof - Google Patents
Germanium tunnelling diode and preparation method thereof Download PDFInfo
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- CN101872723B CN101872723B CN201010180596.XA CN201010180596A CN101872723B CN 101872723 B CN101872723 B CN 101872723B CN 201010180596 A CN201010180596 A CN 201010180596A CN 101872723 B CN101872723 B CN 101872723B
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- germanium
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000004528 spin coating Methods 0.000 claims abstract description 7
- 239000004411 aluminium Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- -1 aluminium germanium Chemical compound 0.000 claims description 6
- 238000001259 photo etching Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910000927 Ge alloy Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000010703 silicon Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004943 liquid phase epitaxy Methods 0.000 abstract 1
- 238000001465 metallisation Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005641 tunneling Effects 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Abstract
The invention provides a germanium tunnelling diode, which has uniform texture and realizes high current density of a tunnelling device and a preparation method thereof. By adopting methods of simple spin coating and doping, metal deposition, plasma chemical vapor deposition, melt quick growth liquid phase epitaxy and the like, the invention provides a low-cost preparation method of the germanium tunnelling diode. The preparation method has the advantages of low cost of material equipment and compatibility with the conventional silicon process. Materials and the method, which are used in the preparation process, are low in cost, nontoxic and harmless; and instruments and the method are widely used for the large-scale integrated industrial manufacturing of industrial silicon.
Description
Technical field
The present invention relates to high-speed semiconductor device and quantum device field, specifically a kind of germanium tunnelling diode and preparation method thereof.
Background technology
Along with the continuous upgrading of Moore's Law asymptotic limit and consumption, the manufacturing method thereof of high speed device has caused the great attention of research institutions and enterprise.And that germanium tunnelling diode has current density is large, operating rate is fast, unique differential negative resistance characteristic, be easy to and the current silicon technology manufacturing technology advantage such as combine, can be widely used in RF radio circuit, high-speed oscillator, memory, in the circuit such as MULTI-VALUED LOGIC CIRCUIT.In the near future, in the silicon device of high speed circuit, will add germanium, or become germanium completely, and the toxicity such as other element GaAs are very large, utilize this element to make high speed device cost very high, be unfavorable for popularizing.At present domestic and international each major company is all at exploitation germanium device technology processing procedure, so germanium tunnelling diode device is star's device of following high speed circuit.
In US Patent No. 6229153, announced a kind of method that the GaAs/ALGaAs/InGaAs of employing material is prepared resonance tunnel-through diode.But the method cost is high, with the problem such as the silicon technology of current main-stream is incompatible, make it be difficult for penetration and promotion again.The preparation method of tunnelling diode that domestic patent 200410006243.2 and patent 2006101472220.2 are announced is all to use vapor phase epitaxial growth method, and this method material cost is expensive, is also difficult for penetration and promotion.
Utilize the process for vapor phase epitaxy slightly unmatched material of bandwidth of growing on three or five compounds of group, to form quantum well, facilitate electron tunneling.The toxic material of three or five compounds of group (for example GaAs) preparation process, high to instrument and the safety requirements of preparation, cause preparation cost too high.Take silicon technology in main large-scale integrated industrial process, because cost and technology capacitive problem, the method that there is no is at present combined San Wu family material and technique with main flow silicon technology simultaneously.These two shortcomings make prior art can only be applied in military grade for special dimension, cannot large-scale application.
Summary of the invention
The object of the invention is to overcome the shortcoming existing in prior art, overcome above-mentioned the deficiencies in the prior art, provide a kind of middle tunneling device current density of the same type the highest germanium tunnelling diode, a kind of germanium tunnelling diode preparation method with low cost is provided simultaneously.
In order to realize above object, the present invention by the following technical solutions:
A preparation method for germanium tunnelling diode, is characterized in that, comprises the steps:
Step 1: use low-doped germanium wafer for substrate, adopt spin coating doping method to make the Substrate Doping Doped n-type germanium wafer of attaching most importance to;
Step 2: adopt metal sedimentation to cover the middle part of heavy doping N-shaped germanium wafer with aluminium;
Step 3: form tableland with wet process after photoetching;
Step 4: using plasma chemical vapour deposition technique deposited silicon nitride covers tableland;
Step 5: adopt rta technique, make the germanium on aluminium and surface be dissolved as liquid, form aluminium Zhe Gong Rong liquid, above cover silicon nitride and make aluminium Zhe Gong Rong liquid keep stable as miniature crucible;
Step 6: cooling after short annealing, form heavy doping p-type germanium, form tunnel-through diode with original weight Doped n-type germanium.
As the preparation method's of germanium tunnelling diode a kind of preferred preparation method, the temperature of rta technique is 500 ℃ to 700 ℃, and aluminium Zhe Gong Rong liquid height is that 100nm is to 120nm.
Further, the temperature of rta technique is preferably 600 ℃, and aluminium Zhe Gong Rong liquid height is preferably 110nm.
As the prepared product of preparation method of germanium tunnelling diode of the present invention, a kind of germanium tunnelling diode, comprises from bottom to top overlapped successively heavy doping N-shaped germanium substrate, heavy doping p-type germanium layer, aluminium germanium alloy layer, silicon nitride compound layer.
As to germanium tunnelling diode product preferably, heavy doping p-type germanium layer height is 50nm-70nm.
As the optimal selection to germanium tunnelling diode product, heavy doping p-type germanium layer height is 60nm.
Preparation method of the present invention is based on germanium, without vapor phase epitaxial growth technique, but utilizes simple spin coating doping, and melt Fast Growth liquid phase epitaxial method, tunnel-through diode made more even, and the tunneling device current density of realization is the highest in of the same type.So it is low that preparation method of the present invention has material installation cost, with the compatible advantage of existing silicon technology, solved the shortcoming of prior art.Preparation process material used is as germanium, spin coating doping, and aluminium cost is not high, nonhazardous.Instrument is manufactured as the large-scale integrated industry that plasma activated chemical vapour deposition and short annealing are all widely used in industrial quarters silicon.
Germanium and silicon belong to the periodic table in same group, all chemical similarity, and therefore, preparation method of the present invention also can be for silicon.
Meanwhile, the invention provides the germanium tunnelling diode that this preparation method of a kind of application obtains, it is more even that this tunnel-through diode is compared existing tunnel-through diode, and the tunneling device current density of realization is the highest in of the same type.
Similarly, the SiGe tunnel-through diode obtaining by preparation method of the present invention, also has similar advantage.
Accompanying drawing explanation
Schematic diagram when Fig. 1 is aluminium lamination covering germanium wafer formation tableland;
Schematic diagram when Fig. 2 is silicon nitride covering tableland;
Fig. 3 is the schematic diagram while forming aluminium Zhe Gong Rong liquid;
Fig. 4 is the schematic diagram of germanium tunnelling diode.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but be not limited to this.
Fig. 1 is respectively the structural representation of germanium tunnelling diode preparation method in different step to Fig. 4.
As shown in Figure 1, the preparation method who describes according to the present invention, using low-doped germanium wafer (Ge) be substrate, employing spin coating doping method makes the Substrate Doping Doped n-type germanium wafer (n+Ge) of attaching most importance to; Then adopt the middle part of metal aluminium (Al) covering heavy doping N-shaped germanium wafer for sedimentation; After photoetching, with wet process, form tableland.The height of aluminium lamination is preferably 100nm, and certainly, the height of aluminium lamination can fluctuate in certain scope, and for example 80nm is also fine between 120nm.
Spin coating refers to that substrate, perpendicular to the axle rotation on self surface, is coated in on-chip technique liquid coating material simultaneously.Semiconductor why can extensive use, and what rely on is exactly that it can change by implant impurity in its lattice that it is electrical, and this process is referred to as doping.Impurity concentration and polarity that doping enters extrinsic semiconductor all can have a huge impact semi-conductive conductive characteristic.Conventionally doping content is higher, and it is better that semi-conductive conductivity will become, and reason is that the electron amount that can enter conduction band can improve and increase along with doping content.The integrated circuit that the semiconductor that doping content is very high can be widely used in because conductivity approaches metal today replaces part metal.High-dopant concentration can add target "+" number on conventionally after n or p.
Photoetching is an industrial step while producing semiconductor element, and this step is transferred to the contour structures being imprinted on photomask on the surface of matrix.General flow is that first on substrate, (the present invention is germanium substrate) is covered with one deck and only counts the metal of nanometer thickness, then on this layer of metal, is covered with one deck photoresist.This layer of photoresist can hardening after photoetching (being generally ultraviolet ray).By photomask only at some local photoresist by photoetching.Photoresist has different types, and some is to all ultraviolet spectrogram sensitization, and some is only to certain photoreception of spectrum, and also some is to X ray or to electron beam sensitization.On silicon, be coated with the photoresist spinner of photoresist.Post-develop resist is dried.Then chip is placed in the solvent of a corroding metal, adopts wet process that the corrosion of metals of not covered by photoresist is fallen.Then use the another kind of special corrosive liquid photoresist of oven dry is got rid of, in stromal surface, just left like this metal that one deck has covered certain area, form tableland.
As shown in Figure 2, be using plasma chemical vapour deposition technique deposited silicon nitride (Si
3n
4) schematic diagram while covering tableland.
Chemical vapour deposition (CVD) (CVD) is the technology that is used for depositing multiple materials being most widely used in semi-conductor industry, comprises large-scale insulating material, most metals material and metal alloy compositions.Principle is: two or more gaseous state raw material import in a reative cell, and then chemical reaction occurs each other for they, forms a kind of new material, deposits in wafer surface.Deposition silicon nitride film (Si
3n
4) be exactly to be formed by silane and nitrogen reaction.For chemical reaction can be carried out at lower temperature, make coating evenly not peel off simultaneously, can utilize the activity of plasma to promote reaction, Here it is plasma chemical vapor deposition.
As shown in Figure 3, be the schematic diagram while carrying out step 5, adopt rta technique, make the germanium on aluminium and surface be dissolved as liquid, (AlGe) Gong Rong liquid, above covers silicon nitride (Si to form aluminium germanium
3n
4) as miniature crucible, make aluminium Zhe Gong Rong liquid keep stable.The temperature of rta technique is preferably 500 ℃ to 700 ℃, and aluminium Zhe Gong Rong liquid height is preferably 100nm to 120nm.The temperature of rta technique of the present invention is preferably 600 ℃, the preferred 110nm of aluminium Zhe Gong Rong liquid height.This step, adopts after rta technique, utilizes melt Fast Growth liquid phase epitaxial method, generates crystal.
As shown in Figure 4, be the schematic diagram of product germanium tunnelling diode of the present invention, cooling after short annealing, form heavy doping p-type germanium (p+Ge), form tunnel-through diode with original weight Doped n-type germanium (n+Ge).
The tunnel-through diode of preparing with method of the present invention, can show obvious differential negative resistance.The more important thing is that can reach peak current density is 120kA/cm
2, be the highest in current density in tunnel-through diode (Esaki tunnel diode) of the same type.Peak current density can be compared or surpass with some resonance tunnel-through diodes based on San Wu family.This product can substitute the expensive tunnel-through diode based on three or five compounds of group and be applied to simulation and Digital Logical Circuits at a high speed.
Obviously above-described embodiment is not limitation of the present invention, and above-mentioned a kind of germanium tunnelling diode and preparation method thereof can also have other many variations.For example preparation method of the present invention is based on germanium, but can, based on silicon, produce silicon tunnel-through diode equally.Although in conjunction with above-mentioned example, discussed the present invention in detail, should be understood that professional person in the industry can expect apparently some are identical, alternative scheme, within all falling into the protection range that the claims in the present invention limit.
Claims (6)
1. a preparation method for germanium tunnelling diode, is characterized in that, comprises the steps:
Step 1: use low-doped germanium wafer for substrate, adopt spin coating doping method to make the Substrate Doping Doped n-type germanium wafer of attaching most importance to;
Step 2: adopt metal sedimentation to cover the middle part of heavy doping N-shaped germanium wafer with aluminium;
Step 3: form tableland with wet process after photoetching;
Step 4: using plasma chemical vapour deposition technique deposited silicon nitride covers tableland;
Step 5: adopt rta technique, make the germanium on aluminium and surface be dissolved as liquid, form aluminium Zhe Gong Rong liquid, above cover silicon nitride and make aluminium Zhe Gong Rong liquid keep stable as miniature crucible;
Step 6: cooling after short annealing, form heavy doping p-type germanium, form tunnel-through diode with original weight Doped n-type germanium.
2. the germanium tunnelling diode obtained of application preparation method as claimed in claim 1, is characterized in that, comprises from bottom to top overlapped successively heavy doping N-shaped germanium substrate, heavy doping p-type germanium layer, aluminium germanium alloy layer, silicon nitride compound layer.
3. preparation method according to claim 1, is characterized in that, the temperature of described rta technique is 500 ℃ to 700 ℃, and described aluminium Zhe Gong Rong liquid height is that 100nm is to 120nm.
4. preparation method according to claim 3, is characterized in that, the temperature of described rta technique is 600 ℃, and described aluminium Zhe Gong Rong liquid height is 110nm.
5. germanium tunnelling diode according to claim 2, is characterized in that, described heavy doping p-type germanium layer height is 50nm-70nm.
6. germanium tunnelling diode according to claim 5, is characterized in that, described heavy doping p-type germanium layer height is 60nm.
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| CN201010180596.XA CN101872723B (en) | 2010-05-24 | 2010-05-24 | Germanium tunnelling diode and preparation method thereof |
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| CN101872723A CN101872723A (en) | 2010-10-27 |
| CN101872723B true CN101872723B (en) | 2014-10-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6229153B1 (en) * | 1996-06-21 | 2001-05-08 | Wisconsin Alumni Research Corporation | High peak current density resonant tunneling diode |
| CN1564325A (en) * | 2004-03-17 | 2005-01-12 | 清华大学 | Hole resonance tunnel-through diode based on Si/SiGe |
| CN101257050A (en) * | 2007-07-06 | 2008-09-03 | 韦文生 | Nanometer silicon hetero-junction bidirectional tunneling diode |
| CN101325223A (en) * | 2008-05-20 | 2008-12-17 | 无锡市纳微电子有限公司 | Nanometer silicon variable capacitance diode and method of processing the same |
| CN101656280A (en) * | 2008-08-22 | 2010-02-24 | 晶元光电股份有限公司 | Luminous element |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6829269B2 (en) * | 2002-05-21 | 2004-12-07 | University Of Massachusetts | Systems and methods using phonon mediated intersubband laser |
-
2010
- 2010-05-24 CN CN201010180596.XA patent/CN101872723B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6229153B1 (en) * | 1996-06-21 | 2001-05-08 | Wisconsin Alumni Research Corporation | High peak current density resonant tunneling diode |
| CN1564325A (en) * | 2004-03-17 | 2005-01-12 | 清华大学 | Hole resonance tunnel-through diode based on Si/SiGe |
| CN101257050A (en) * | 2007-07-06 | 2008-09-03 | 韦文生 | Nanometer silicon hetero-junction bidirectional tunneling diode |
| CN101325223A (en) * | 2008-05-20 | 2008-12-17 | 无锡市纳微电子有限公司 | Nanometer silicon variable capacitance diode and method of processing the same |
| CN101656280A (en) * | 2008-08-22 | 2010-02-24 | 晶元光电股份有限公司 | Luminous element |
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