CN106229257A - A kind of molecular layer doping method realizing super abrupt dopant gradient and an ultra shallow junction depth - Google Patents
A kind of molecular layer doping method realizing super abrupt dopant gradient and an ultra shallow junction depth Download PDFInfo
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- CN106229257A CN106229257A CN201610649282.7A CN201610649282A CN106229257A CN 106229257 A CN106229257 A CN 106229257A CN 201610649282 A CN201610649282 A CN 201610649282A CN 106229257 A CN106229257 A CN 106229257A
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- organic molecule
- doped structure
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- junction depth
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
Abstract
The invention discloses a kind of molecular layer doping method, including: remove contamination and the natural oxidizing layer treating doped structure surface, expose the hydrogen bond treating doped structure surface；Treating doped structure surface cover one layer of impure element organic molecule, this organic molecule with treat doped structure surface formed covalent bond is combined, as adulterate impurity source；Deposit cap, the purpose of impurity element external diffusion during to reach to prevent from annealing；Make the impurity element in organic molecule enter by annealing to treat doped structure, form super precipitous doping gradient and an ultra shallow junction depth；Remove organic molecule and cap；Thus prepare super abrupt dopant gradient and the device of an ultra shallow junction depth in integrated circuit, there is higher doping content and impurity activation rate, can significantly relax the requirement to subsequent annealing process, technique is simple, cost price is little, it is possible to meets and realizes super abrupt dopant gradient and the requirement of an ultra shallow junction depth in small size device.
Description
Technical field
The invention belongs to super large-scale integration manufacturing technology field, relate to a kind of forming super in integrated circuit precipitous mix
The molecular layer doping method of miscellaneous gradient and an ultra shallow junction depth.
Background technology
From transistor invention five ten years till now, integrated circuit follows Moore's Law development always, it may be assumed that in price
In the case of constant, the integrated level of integrated circuit, within every 18 months, double, performance boost one times.As time goes on,
The characteristic size of semiconductor device narrows down to nanoscale from submicron-scale, and doping techniques is carried by reducing of device size
Go out the biggest challenge, according to the requirement of ITRS 2013, the multi-gate device of 11nm a length of for grid, the junction depth palpus of source and drain extension
It is reduced to 6.1nm, and the impurity concentration gradient of source and drain extension is only 1.4nm/dec, therefore, how to realize an ultra shallow junction depth, surpass
Abrupt dopant gradient becomes industry problem demanding prompt solution.
Existing two traditional big doping process are diffusion and ion implanting, spread owing to process time length, impurity laterally expand
The inferior position potassium hydroxides such as scattered serious, lack of homogeneity, in the preparation of nanoscale integrated circuit, the substitute is ion implanting skill
Art.But ion implanting shallow junction to be realized must use the Implantation Energy that heavy ion is incident and ultralow, heavy ion can introduce bigger
Lattice damage, and low energy ion beam implantation easily causes channelling effect and from splash effect.Further, since ion implanting exists one
The range deviation of individual change at random, is the most also unfavorable for realizing abrupt dopant distribution.These weak points all significantly limit
Ion implanting application in prepared by nanoscale devices.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention provides a kind of and forms super abrupt dopant gradient in integrated circuit
Molecular layer doping method with an ultra shallow junction depth, it is possible to meet and realize super abrupt dopant gradient and an ultra shallow junction depth in small size device
Requirement.
Present invention provide the technical scheme that
A kind of molecular layer doping method, for preparing super abrupt dopant gradient and the small size device of an ultra shallow junction depth；Including
Following steps:
1) contamination and the natural oxidizing layer on doped structure surface is treated in removal, exposes the hydrogen bond treating doped structure surface；
2) treating doped structure surface cover one layer of impure element organic molecule, this organic molecule with treat doped structure
Surface forms covalent bond and combines, as the impurity source of doping；
3) deposit cap, impurity element external diffusion when its objective is to prevent from annealing；
4) annealing, its objective is that making the impurity element in organic molecule enter treats doped structure, forms super precipitous doping
Gradient and an ultra shallow junction depth；
5) organic molecule and cap are removed.
Further, step 1) described in treat that doped structure can be the semi-conducting material such as silicon, germanium, it is also possible to be graphite
The two-dimensional material such as alkene, molybdenum bisuphide；Can be substrate, it is also possible to be other structure needing to mix impurity such as source and drain, raceway groove；
Further, step 1) in remove surface contamination method can be organic washing, concentrated sulphuric acid clean, fuming nitric aicd
Cleaning, ammonia and hydrogen peroxide mixing cleaning etc.；
Further, step 1) in remove surface oxide layer method can be hydrochloric acid cleaning, hydrofluoric acid clean etc.；
Further, step 2) in organic molecule must contain and need the impurity element of doping, and during subsequent anneal,
Impurity element can be driven into treats that doped structure forms electrical activation, and such as: when mixing p type impurity, organic molecule is the allyl containing boron element
Ylboronic acid pinacol ester (allylboronic acid pinacol ester, ABAPE), during doped type N impurity, organic molecule is
Diethyl 1-propyl phosphonous acid ester (diethyl 1-propylphosphonate, DPP) etc. of phosphorus element-containing；
Further, step 2) in the method treating that doped structure surface covers one layer of organic molecule, be by organic molecule
It is dissolved in high-flash solution (such as 1，3，5-trimethyl-benzene), is then spin coated onto treating on doped structure, finally in dry anaerobic
React under 100-200 DEG C of environment 2-3 hour, i.e. available only with treat that doped structure surface forms organic point of a thin layer of covalent bond
Son；
Further, step 3) described in cap must with treat that doped structure does not occur chemical reaction, the finest and close
Property good, when can stop subsequent anneal, the impurity element in organic molecule is to external diffusion, such as silicon oxide, aluminium oxide, hafnium oxide etc.,
Preferential oxidation silicon；
Further, step 3) described in cap deposition process can be atomic layer deposition (Atomic Layer
Deposition), low-pressure chemical vapor phase deposition (Low Pressure Chemical Vapor Deposition), plasma
Strengthen chemical vapor deposition (Plasma Enhanced Chemical Vapor Deposition), inductively coupled plasma
Strengthen chemical vapor deposition (Inductively Coupled Plasma Enhance Chemical Vapor
Deposition), sputtering etc..
Further, step 4) described in annealing can be rapid thermal annealing (Rapid Thermal Annealing),
Spike annealing (Spike Annealing), annealing of glittering (Flash Annealing), laser annealing (Laser Anealing)
Etc. advanced anneal techniques, the time of annealing and temperature determine according to designed doping content and junction depth, and temperature is the highest, the time
The longest, the doping content obtained is the highest, and junction depth is the deepest.
Further, step 5) in remove the method for organic molecule and cap and can use wet corrosion technique, such as,
When cap is silicon oxide, and organic molecule is ABAPE, corrosive liquid can use Fluohydric acid., is removed at normal temperatures.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention provides a kind of and forms super abrupt dopant gradient and the molecular layer doping method of an ultra shallow junction depth in integrated circuit,
The advantage that the method has following several respects:
A) can realize junction depth less than 2nm, impurity concentration gradient is that an ultra shallow junction depth of 0.6nm/dec, super abrupt dopant are divided
Cloth, meets the small size device requirement to doping process.
B) compare doping in situ, ion implantation doping combines laser annealing, ion implantation doping combines the skills such as spike annealing
Art, has higher doping content and impurity activation rate.
C) being the Organic Monolayers on Flat containing doped chemical due to impurity source, the doping process being not as routine needs like that
The annealing time of Millisecond forms shallow junction, therefore can significantly relax the requirement to subsequent annealing process.
D) to the two-dimensional material such as Graphene, molybdenum bisuphide, and nano wire, this one-dimentional structure of CNT, still can
Carrying out Effective Doping, this ion implantation technology being traditional is difficult to.
E) compare ion implantation technology, there is not the problems such as lattice damage, channelling effect and range deviation.
F) mutually the most compatible with Bulk CMOS technique, technique is simple, and cost price is little.
Accompanying drawing explanation
Fig. 1-6 represents the technological process that the molecular layer that the present invention proposes adulterates respectively；Wherein:
Fig. 1 is to remove to stain and natural oxidizing layer；
Fig. 2 is the organic molecule covering one layer of impure element；
Fig. 3 is deposit cap；
Fig. 4 is annealing；
Fig. 5 is to remove organic molecule and cap；
Fig. 6 is the legend of Fig. 1～Fig. 5；
Fig. 7 be utilize use molecular layer doping method that silicon substrate is carried out in embodiment of the present invention secondary that boron-doping obtains from
Sub-mass spectrum (SIMS) figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings, further describe the present invention by embodiment, but limit the model of the present invention never in any form
Enclose.
The present invention proposes a kind of molecular layer doping method realizing super abrupt dopant gradient and an ultra shallow junction depth, and the method can
Meet and small size device realizes super abrupt dopant gradient and the requirement of an ultra shallow junction depth；Comprise the following steps:
1) contamination and the natural oxidizing layer on doped structure surface is treated in removal, exposes the hydrogen bond treating doped structure surface；
Wherein, treat that doped structure can be the semi-conducting material such as silicon, germanium, it is also possible to be the two dimension such as Graphene, molybdenum bisuphide
Material；Can be substrate, it is also possible to be other structure needing to mix impurity such as source and drain, raceway groove；The method removing surface contamination
Can be organic washing, concentrated sulphuric acid cleaning, fuming nitric aicd cleaning, ammonia and hydrogen peroxide mixing cleaning etc.；Remove surface oxide layer
Method can be hydrochloric acid cleaning, hydrofluoric acid clean etc.；
2) treating doped structure surface cover one layer of impure element organic molecule, this organic molecule with treat doped structure
Surface forms covalent bond and combines, as the impurity source of doping；
Wherein, organic molecule must contain the impurity element needing to be adulterated, and during subsequent anneal, impurity element energy quilt
Driving in and treat that doped structure forms electrical activation, such as: when mixing p type impurity, organic molecule is the pi-allyl boric acid pinacol containing boron element
Ester (allylboronic acid pinacol ester, ABAPE), during doped type N impurity, organic molecule is the two of phosphorus element-containing
Ethyl 1-propyl phosphonous acid ester (diethyl 1-propylphosphonate, DPP) etc.；
Further, in the method treating that doped structure surface covers one layer of organic molecule in step 2, it is that organic molecule is molten
Solution, in high-flash solution (such as 1，3，5-trimethyl-benzene), is then spin coated onto treating on doped structure, finally in dry anaerobic
React under 100-200 DEG C of environment 2-3 hour, i.e. available only with treat that doped structure surface forms organic point of a thin layer of covalent bond
Son；
3) deposit cap, impurity element external diffusion when its objective is to prevent from annealing；
Wherein, must there is not chemical reaction with treating doped structure in cap, compactness is good simultaneously, can stop follow-up moving back
During fire, the impurity element in organic molecule is to external diffusion, such as silicon oxide, aluminium oxide, hafnium oxide etc., preferential oxidation silicon；
Further, the cap deposition process described in step 3 can be atomic layer deposition (Atomic Layer
Deposition), low-pressure chemical vapor phase deposition (Low Pressure Chemical Vapor Deposition), plasma
Strengthen chemical vapor deposition (Plasma Enhanced Chemical Vapor Deposition), inductively coupled plasma
Strengthen chemical vapor deposition (Inductively Coupled Plasma Enhance Chemical Vapor
Deposition), sputtering etc..
4) annealing, its objective is that making the impurity element in organic molecule enter treats doped structure, forms super precipitous doping
Gradient and an ultra shallow junction depth；
Wherein, annealing can be rapid thermal annealing (Rapid Thermal Annealing), spike annealing (Spike
Annealing), annealing of glittering (Flash Annealing), the advanced anneal techniques such as laser annealing (Laser Anealing),
Time and the temperature of annealing determine according to designed doping content and junction depth, and temperature is the highest, and the time is the longest, the doping obtained
Concentration is the highest, and junction depth is the deepest.
5) organic molecule and cap are removed.
Further, the method for organic molecule and cap removed in step 5 can use wet corrosion technique, such as,
When cap is silicon oxide, and organic molecule is ABAPE, corrosive liquid can use Fluohydric acid., is removed at normal temperatures.
Following example realize impurity concentration gradient and the ultra-shallow junctions of 2nm of the 0.6nm/dec of boron-doping on body silicon substrate
Deeply, realize according to the following step:
1) utilize fuming nitric aicd to wash away contamination on 4 cun of N-type (100) body silicon substrates, then wash away autoxidation with Fluohydric acid.
Layer, as shown in Figure 1；
2) the organic molecule ABAPE containing boron element is dissolved in 1，3，5-trimethyl-benzene, is spin-coated to substrate surface, dry
Reaction 2.5 hours under 120 DEG C of environment of dry anaerobic, as shown in Figure 2；
3) PECVD 50nm SiO2 is as cap, as shown in Figure 3；
4) using RTA 950 DEG C, anneal 5s, and the boron element in ABAPE is driven into substrate, forms impurity concentration gradient and is
0.6nm/dec and junction depth are the dopant profiles of 2nm, as shown in Figure 4；
5) removing organic molecule and SiO2 with the solution that proportioning is HF:H2O=1:20, etching time is 10min, such as Fig. 5
Shown in；
The impurity concentration gradient of the final 0.6nm/dec realizing boron-doping on body silicon substrate and an ultra shallow junction depth of 2nm, pass through
SIMS (secondary ion mass spectrum) figure of Fig. 7 is it is found that the impurity concentration gradient of the boron-doping prepared and an ultra shallow junction depth all reach little
The scale device requirement to doping.
It should be noted that publicizing and implementing the purpose of example is that help is further appreciated by the present invention, but the skill of this area
Art personnel are understood that various substitutions and modifications are all without departing from the present invention and spirit and scope of the appended claims
Possible.Therefore, the present invention should not be limited to embodiment disclosure of that, and the scope of protection of present invention is with claim
Book defines in the range of standard.
Claims (10)
1. a molecular layer doping method, for preparing super abrupt dopant gradient and the small size device of an ultra shallow junction depth；Including such as
Lower step:
1) contamination and the natural oxidizing layer on doped structure surface is treated in removal, exposes the hydrogen bond treating doped structure surface；
2) treating doped structure surface cover one layer of impure element organic molecule, this organic molecule with treat doped structure surface
Formation covalent bond combines, as the impurity source of doping；
3) deposit cap, the purpose of impurity element external diffusion during to reach to prevent from annealing；
4) make the impurity element in organic molecule enter by annealing to treat doped structure, form super precipitous doping gradient and an ultra shallow
Junction depth；
5) organic molecule and cap are removed；
Thus prepare super abrupt dopant gradient and the device of an ultra shallow junction depth.
2. as claimed in claim 1 molecular layer doping method, is characterized in that, step 1) described in treat that doped structure uses the material to be
Silicon or Germanium semiconductor material, or use Graphene or molybdenum bisuphide two-dimensional material；Described treat doped structure be substrate, source and drain or
Channel structure；The minimizing technology of described surface contamination includes that organic washing, concentrated sulphuric acid clean, fuming nitric aicd cleans, ammonia and double
The mixing of oxygen water is cleaned；The minimizing technology of described surface oxide layer includes hydrochloric acid cleaning, hydrofluoric acid clean.
3. as claimed in claim 1 molecular layer doping method, is characterized in that, step 2) described organic molecule must contain and need doping
Impurity element, and during subsequent anneal, impurity element is driven into treats that doped structure forms electrical activation.
4. molecular layer doping method as claimed in claim 3, is characterized in that, when mixing p type impurity, organic molecule is containing boron element
Pi-allyl pinacol borate；When doped type N impurity, organic molecule is the diethyl 1-propyl phosphonous acid ester of phosphorus element-containing.
5. as claimed in claim 1 molecular layer doping method, is characterized in that, step 2) described treating that doped structure surface covers one
The method of layer organic molecule, is specifically dissolved in organic molecule in high-flash solution, is then spin coated onto treating on doped structure,
After in the environment of dry anaerobic react a period of time, obtain only with treat doped structure surface formation covalent bond a thin layer organic
Molecule.
6. molecular layer doping method as claimed in claim 5, is characterized in that, described high-flash solution is 1，3，5-trimethyl-benzene；
The temperature of the environment of described anaerobic is 100-200 DEG C；In the environment of dry anaerobic, the time of reaction is 2-3 hour.
7. molecular layer doping method as claimed in claim 1, is characterized in that, step 3) described cap selection silicon oxide, oxidation
Aluminum or hafnium oxide；Described cap with treat that doped structure does not occur chemical reaction, compactness is good, has when can stop subsequent anneal
Impurity element in machine molecule is to external diffusion.
8. molecular layer doping method as claimed in claim 7, is characterized in that, described cap deposition process is atomic layer deposition side
Method, low-pressure chemical vapor phase deposition method, plasma body reinforced chemical vapor deposition method, inductively coupled plasma strengthen chemistry
Gas-phase deposition method or sputtering method.
9. as claimed in claim 1 molecular layer doping method, is characterized in that, step 4) described in be annealed into rapid thermal annealing, spike
Anneal, glitter annealing or laser anneal method；The temperature of annealing is the highest, and the time is the longest, and the doping content obtained is the highest, and junction depth is more
Deeply.
10. as claimed in claim 1 molecular layer doping method, is characterized in that, step 5) described removal organic molecule and cap
Method use wet corrosion technique.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4619719A (en) * | 1982-01-28 | 1986-10-28 | Owens-Illinois, Inc. | Process for forming a doped oxide film and composite article |
| WO2011112546A1 (en) * | 2010-03-08 | 2011-09-15 | Dynaloy, Llc | Methods and compositions for doping silicon substrates with molecular monolayers |
| WO2014034217A1 (en) * | 2012-08-27 | 2014-03-06 | 大日本スクリーン製造株式会社 | Substrate treating method and substrate treating device |
| CN105023833A (en) * | 2014-04-30 | 2015-11-04 | 加利福尼亚大学董事会 | Doping of a substrate via a dopant containing polymer film |
-
2016
- 2016-08-10 CN CN201610649282.7A patent/CN106229257A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4619719A (en) * | 1982-01-28 | 1986-10-28 | Owens-Illinois, Inc. | Process for forming a doped oxide film and composite article |
| WO2011112546A1 (en) * | 2010-03-08 | 2011-09-15 | Dynaloy, Llc | Methods and compositions for doping silicon substrates with molecular monolayers |
| WO2014034217A1 (en) * | 2012-08-27 | 2014-03-06 | 大日本スクリーン製造株式会社 | Substrate treating method and substrate treating device |
| CN105023833A (en) * | 2014-04-30 | 2015-11-04 | 加利福尼亚大学董事会 | Doping of a substrate via a dopant containing polymer film |
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Application publication date: 20161214 |