CN104557999A - Novel thin film deposition aluminum precursor and preparation method thereof - Google Patents
Novel thin film deposition aluminum precursor and preparation method thereof Download PDFInfo
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- CN104557999A CN104557999A CN201510067153.2A CN201510067153A CN104557999A CN 104557999 A CN104557999 A CN 104557999A CN 201510067153 A CN201510067153 A CN 201510067153A CN 104557999 A CN104557999 A CN 104557999A
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- thin film
- aluminium
- aluminum
- presoma
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000427 thin-film deposition Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000002243 precursor Substances 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 150000004767 nitrides Chemical class 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims description 38
- 239000010408 film Substances 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- -1 aluminium alkane Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005138 cryopreservation Methods 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 2
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 229910000086 alane Inorganic materials 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 7
- ZBNJVQZTBKMTRK-UHFFFAOYSA-N n-butylpyridin-2-amine Chemical compound CCCCNC1=CC=CC=N1 ZBNJVQZTBKMTRK-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018173 Al—Al Inorganic materials 0.000 description 1
- 229910018509 Al—N Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000033240 Progressive symmetric erythrokeratodermia Diseases 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/12—Deposition of aluminium only
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a novel thin film deposition aluminum precursor. The novel thin film deposition aluminum precursor has a molecular structure expressed by a structural formula (I) as shown in the specification, wherein R1, R2, R3, R4 and R5 represent hydrogen atom, C1-C6 alkyls, C2-C5 alkenyls, C3-C10 naphthenic bases, C6-C10 aryls or -Si(R0)3, and halogen substituent groups of the groups, wherein R0 is one of C1-C6 alkyls or the halogen substituent groups thereof; and R1, R2, R3, R4 and R5 are the same or different. According to the novel thin film deposition aluminum precursor, the thin film deposition precursor good in thermal stability and not easy to decompose is developed, and is convenient to store and transport and good in high-temperature volatility; aluminum-containing thin films such as an aluminum-containing metal thin film, an aluminum-containing oxide thin film, an aluminum-containing nitride thin film and an aluminum-containing alloy thin film can be prepared by use of a CVD/ALD process, and the film-forming property is excellent.
Description
Technical field
The present invention relates to a kind of novel thin film deposition of aluminum presoma and its production and use, be particularly useful for technique for atomic layer deposition, relate to semi-conductor and field of nanometer technology.Specifically, relate to a kind of stable in properties, not easily decompose, high-temperature volatile is excellent, is convenient to the thin film deposition aluminium precursor species storing and transport.
Background technology
Along with the fast development of semiconductor technology, manufacture craft and the technology of device also there occurs change, film is employed more and more, the manufacturing technology of respective films is also updated thereupon, chemical vapour deposition (CVD) has many advantages compared with conventional art, and ald (ALD) technology has larger advantage in some fields.
In CVD/ALD Technology, the character of presoma is most important.At normal temperatures, presoma should have higher stability, so that produce, transport and store; Also should there is higher volatility, to make presoma enter sediment chamber with carrier gas simultaneously.In addition, for CVD presoma, good thermal decomposition performance should be had at higher temperature (depositing temperature), to deposit suitable film; For ALD presoma, at higher temperature (depositing temperature), still should there is higher thermostability to avoid the thermolysis of self, have with another provenance reactive to deposit film forming preferably simultaneously.Due to the rigors to character such as presoma stability, volatility, really can be used in the presoma of film forming and seldom, invent one of suitable presoma gordian technique becoming CVD/ALD.
With regard to aluminium and the deposition technique containing aluminium film, the stability of aluminium presoma is a technical barrier of the art always.Abroad, US Patent No. 20030224152A1 in 2003 discloses the CVD presomas such as the mixture of a series of aluminum alkyls, aluminium alkane and amine; Within 2007, patent WO2007/136184A1 discloses aminoboranes base aluminium alkane mixture as CVD presoma.And in ALD technology, the presoma used also is all the aforesaid limited precursor that these are applied in CVD.At home, number of patent application 201310450417.3 discloses a kind of method by ALD deposition techniques pellumina, and presoma is also aluminum alkyls (trimethyl aluminium).Above-mentioned aluminium presoma has good volatility, is widely used in existing CVD/ALD technology, but all there is following problem:
(1) normal temperature all easily decomposes, character extremely unstable, high to the equipment requirements stored, and in storage process, decomposable asymmetric choice net generates hydrogen and metallic aluminium, and metallic aluminium is cartalytic decomposition effect conversely, has the danger of blasting, and is unfavorable for storing, transporting and follow-up use.
(2) passing through in ALD deposit film process, the thermal stability due to presoma is not good and pyrolysis occurs, and along with there occurs CVD, seriously limits the advantage of ALD.
Summary of the invention
The present invention is that the shortcoming existed to overcome above-mentioned prior art proposes, its technical problem solved is to provide stable in properties under a series of normal temperature, not easily decompose, be convenient to store and transport, and in actual application volatility excellent, there is not thermolysis, be applicable to the aluminium presoma of ALD technology, and the preparation method of this presoma and purposes.
The invention provides a kind of novel thin film deposition of aluminum presoma, it is characterized in that there is the molecular structure of structural formula (I):
Wherein, R
1, R
2, R
3, R
4, R
5represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5identical or different.
Present invention also offers a kind of method preparing novel thin film deposition of aluminum presoma as above, it is characterized in that reacting according to following chemical formula:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11identical or different.
Wherein, comprise the following steps: the second reactant comprising aluminium alkane is placed in reaction vessel by (1), solubilizing agent stirs, and is added under cryogenic in reaction vessel by the first reactant comprising amido pyridine or derivatives thereof, and stirring at room temperature or heated and stirred reaction are spent the night; (2) filtered by the mixture in step (1), low pressure concentrates, and obtains the solidliquid mixture of seldom amount, adds solvent, hold over night, obtain colourless bulk crystals, be presoma (I).
Wherein, the temperature of cold condition and/or cryopreservation is-78 DEG C to 0 DEG C, uses and is selected from liquid nitrogen, dry ice, liquefied ammonia, any one cooling way of cold cycle pump and combination thereof.
Wherein, the time of stirring at room temperature or heated and stirred is 1 to 10 hour.
Wherein, the temperature of stirring at room temperature or heated and stirred is 25 DEG C to 150 DEG C.
Wherein, the molar ratio of the first reactant and the second reactant is 1.0:1.0 to 1.0:3.0.
Wherein, solvent is selected from any one and combination of following organic solvent: be selected from C
5h
12~ C
8h
18straight or branched alkane, C
5h
10~ C
8h
16the alkane of cyclic alkane; Be selected from the aromatic hydrocarbon of benzene, toluene; Be selected from the ethers of ether, tetrahydrofuran (THF).
Wherein, the condition of reaction mixture filtering and concentrating is: concentrated 25 ~ 80 DEG C of pressurizations, pressure is 0.05 ~ 0.20MPa.
The present invention still further provides a kind of method, semi-conductor device manufacturing method, comprise and adopt the film of CVD or ALD technique preparation containing aluminium element, described film adopts aluminium presoma as above manufacture, wherein, described film comprises aluminum metal film, the sull containing aluminium, the nitride film containing aluminium, any one and combination containing the alloy firm of aluminium.
Beneficial effect of the present invention comprises:
(1) introduce pyridine ring as part, effectively reduce the activity of presoma, and can be generated the precursor compound of larger molecular weight by Al-Al, Al-N key, stability improves, volatility reduces, and is convenient to store and transport.
(2) building-up process easy clean, raw material is cheap, and energy consumption is low, is a kind of preparation method of environmental protection and economy.
(3) film forming properties is excellent, and scanning electron microscope (SEM) Fig. 2 containing aluminium film obtained for aluminium source for the presoma of preparation in embodiment one, film forming is even and fine and close.
This thin film deposition aluminium presoma effectively overcomes the shortcoming of prior art, improves the efficiency of deposit film, is widely used in semi-conductor and field of nanometer technology.
Accompanying drawing explanation
Technical scheme of the present invention is described in detail referring to accompanying drawing, wherein:
Fig. 1 shows the compound [Al preparing embodiment one according to the present invention
2h
2{ N (2-C
5h
4n) n-Bu}
2] thermogravimetric analysis collection of illustrative plates, wherein, atlas analysis: weightless starting point temperature is 183.4 DEG C, the temperature of weightless 50% correspondence is 284.6 DEG C, and weightless terminating point temperature is 311.8 DEG C, and residual mass is 1.76%.
Fig. 2 show with the presoma of preparation in embodiment one for aluminium source obtain containing aluminium film scanning Electronic Speculum (SEM) figure.
Fig. 3 shows the thermogravimetric analysis collection of illustrative plates of front three amine alane (TMAA), and wherein, atlas analysis: start volatile weight loss under room temperature, the temperature of weightless 50% correspondence is 86.3 DEG C, and weightless terminating point temperature is 111.5 DEG C, and residual mass is 6.2%.
Fig. 4 shows the thermogravimetric analysis collection of illustrative plates of dimethyl amine aluminium alkane (DMEAA), and wherein, atlas analysis: start volatile weight loss under room temperature, the temperature of weightless 50% correspondence is 115.1 DEG C, and weightless terminating point temperature is 134.4 DEG C, and residual mass is 7.1%.
Fig. 5 shows the thermogravimetric analysis collection of illustrative plates of dimethyl hydrogenated aluminium alkane (DMAH), and wherein, atlas analysis: start volatile weight loss under room temperature, the temperature of weightless 50% correspondence is 124.9 DEG C, and weightless terminating point temperature is greater than 200 DEG C, and residual mass is 26.6%.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.
This novel thin film deposition precursor body as above is usually used in various deposited film in semiconductor applications and field of nanometer technology, as aluminium film, pellumina, composite metal membrane and nano thin-film.This presoma stable in properties provided by the invention, not easily decomposes, and is convenient to store and transport, and high-temperature volatile is good, and film forming properties is excellent, facilitates the development of semi-conductor and nanotechnology.
The invention provides a series of aluminium presoma as shown in structural formula (I):
Wherein, R
1, R
2, R
3, R
4, R
5represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5identical or different.
Structural formula (I) presoma can be synthesized by following chemical equation (1) by the pyridine and its derivatives of easily acquisition and aluminium alkane:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11identical or different.
The preparation of structural formula (I) precursor compound comprises the following steps: that the second reactant comprising aluminium alkane is placed in reaction vessel by (1), solubilizing agent stirs, added under cryogenic in reaction vessel by the first reactant comprising amido pyridine or derivatives thereof, stirring at room temperature or heated and stirred reaction are spent the night; (2) filtered by the mixture in step (1), low pressure concentrates, and obtains the solidliquid mixture of seldom amount, adds solvent, hold over night, obtain colourless bulk crystals, be presoma (I).
Wherein, the temperature of described cold condition and/or cryopreservation is-78 DEG C to 0 DEG C, uses and is selected from liquid nitrogen, dry ice, liquefied ammonia, any one cooling way of cold cycle pump and combination thereof; The time of described stirring at room temperature or heated and stirred is 1 to 10 hour; The temperature of described stirring at room temperature or heated and stirred is 25 DEG C to 150 DEG C; The molar ratio of described first reactant and the second reactant is 1.0:1.0 to 1.0:3.0; Described solvent is selected from any one and combination of following organic solvent: be selected from C
5h
12~ C
8h
18straight or branched alkane, C
5h
10~ C
8h
16the alkane of cyclic alkane; Be selected from the aromatic hydrocarbon of benzene, toluene; Be selected from the ethers of ether, tetrahydrofuran (THF); The condition of described reaction mixture filtering and concentrating is: concentrated 25 ~ 80 DEG C of pressurizations, pressure is 0.05 ~ 0.20MPa.
By above-mentioned aluminium presoma (I), the film adopting CVD/ALD technique to obtain, can comprise aluminium film, pellumina, aluminium alloy film etc. containing aluminium film.In addition, the application of the above-mentioned film of acquisition comprises, metal interlevel interconnection, contact plunger, device terminal (source electrode, drain electrode, grid), device height K insulation layer (gate insulator of such as MOSFET).
Below, applicant has done some specific experiments to the present invention, with compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2] be prepared as example, and with front three amine alane (TMAA), dimethyl amine aluminium alkane (DMEAA) and dimethyl hydrogenated aluminium (DMAH) Progressive symmetric erythrokeratodermia verify ratio, only for elaborating the present invention, and limit scope of invention never in any form.
(1) embodiment one:
Front three amine alane 10.0mmol is placed in reaction vessel, add after normal hexane stirs, slowly added in system under low temperature-78 DEG C of conditions by the 2-n-butylamino pyridine 10.0mmol being dissolved in toluene, in dropping process, system becomes dark green translucent and emerge with bubble.After stirring at room temperature 1h, be heated to 25 DEG C of backflows and spend the night; Filtered by the mixture obtained, under low pressure 0.05MPa condition, concentrated at temperature 25 DEG C, obtain the solidliquid mixture of seldom amount, add normal hexane, there is a large amount of precipitation in system, hold over night immediately, obtains colourless bulk crystals, is compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2], productive rate 87%, numbering is designated as 1#.
(2) embodiment two:
Front three amine alane 15.0mmol is placed in reaction vessel, add after normal hexane stirs, slowly added in system under low temperature-56 DEG C of conditions by the 2-n-butylamino pyridine 10.0mmol being dissolved in toluene, in dropping process, system becomes dark green translucent and emerge with bubble.After stirring at room temperature 3h, be heated to 75 DEG C of backflows and spend the night; Filtered by the mixture obtained, under low pressure 0.1MPa condition, concentrated under temperature 45 C, obtain the solidliquid mixture of seldom amount, add normal hexane, there is a large amount of precipitation in system, hold over night immediately, obtains colourless bulk crystals, is compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2], productive rate 88%, numbering is designated as 2#.
(3) embodiment three:
Front three amine alane 20.0mmol is placed in reaction vessel, add after normal hexane stirs, slowly added in system under low temperature-39 DEG C of conditions by the 2-n-butylamino pyridine 10.0mmol being dissolved in toluene, in dropping process, system becomes dark green translucent and emerge with bubble.After stirring at room temperature 5h, be heated to 105 DEG C of backflows and spend the night; Filtered by the mixture obtained, under low pressure 0.1MPa condition, concentrated under temperature 60 C, obtain the solidliquid mixture of seldom amount, add normal hexane, there is a large amount of precipitation in system, hold over night immediately, obtains colourless bulk crystals, is compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2], productive rate 86%, numbering is designated as 3#.
(4) embodiment four:
Front three amine alane 25.0mmol is placed in reaction vessel, add after normal hexane stirs, slowly added in system under low temperature-25 DEG C of conditions by the 2-n-butylamino pyridine 10.0mmol being dissolved in toluene, in dropping process, system becomes dark green translucent and emerge with bubble.After stirring at room temperature 8h, be heated to 150 DEG C of backflows and spend the night; Filtered by the mixture obtained, under low pressure 0.15MPa condition, concentrated at temperature 75 DEG C, obtain the solidliquid mixture of seldom amount, add normal hexane, there is a large amount of precipitation in system, hold over night immediately, obtains colourless bulk crystals, is compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2], productive rate 88%, numbering is designated as 4#.
(5) embodiment five:
Front three amine alane 30.0mmol is placed in reaction vessel, add after normal hexane stirs, slowly added in system under low temperature 0 DEG C of condition by the 2-n-butylamino pyridine 10.0mmol being dissolved in toluene, in dropping process, system becomes dark green translucent and emerge with bubble.After stirring at room temperature 10h, be heated to 150 DEG C of backflows and spend the night; Filtered by the mixture obtained, under low pressure 0.2MPa condition, concentrated at temperature 80 DEG C, obtain the solidliquid mixture of seldom amount, add normal hexane, there is a large amount of precipitation in system, hold over night immediately, obtains colourless bulk crystals, is compound [Al
2h
2{ N (2-C
5h
4n) n-Bu}
2], productive rate 87%, numbering is designated as 5#.
Table 1
As shown in Table 1, by the thin film precursor compound [Al of preparation
2h
2{ N (2-C
5h
4n) n-Bu}
2] (1#, 2#, 3#, 4#, 5#) and aluminium presoma of the prior art contrast, TMAA, DMEAA and DMAH all start volatile weight loss under room temperature condition, final residue is all higher than 6.0%, even reach 26.6%, illustrate that these three kinds of aluminium presoma high temperature very easily decompose, character is unstable, and hazard level is high.And the temperature of the weightless starting point of new aluminium presoma provided by the invention is at about 183 DEG C, weightless 50% temperature is about 284 DEG C, and final residue is down to 1.7%, shows higher thermostability, especially more stable under normal temperature, is convenient to store and transport.
Although the present invention is described with reference to one or more exemplary embodiment, those skilled in the art can know without the need to departing from the scope of the invention and make various suitable change and equivalents to technical process or material structure.In addition, can be made by disclosed instruction and manyly may be suitable for the amendment of particular condition or material and not depart from the scope of the invention.Therefore, object of the present invention does not lie in and is limited to as realizing preferred forms of the present invention and disclosed specific embodiment, and disclosed materials chemistry formula structure and manufacture method thereof will comprise all embodiments fallen in the scope of the invention.7 -->
Claims (10)
1. a novel thin film deposition of aluminum presoma, is characterized in that, has the molecular structure of structural formula (I):
Wherein, R
1, R
2, R
3, R
4, R
5represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5identical or different.
2. prepare a method for a kind of novel thin film deposition of aluminum presoma as claimed in claim 1, it is characterized in that reacting according to following chemical formula:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11represent hydrogen atom, C
1~ C
6alkyl, C
2~ C
5alkenyl, C
3~ C
10cycloalkyl, C
6~ C
10aryl or-Si (R
0)
3, and the halogen substiuted group of above-mentioned group, wherein R
0for C
1~ C
6alkyl or its halogen substiuted group, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11identical or different.
3. method as claimed in claim 2, wherein, comprises the following steps:
(1) the second reactant comprising aluminium alkane is placed in reaction vessel, solubilizing agent stirs, and is added under cryogenic in reaction vessel by the first reactant comprising amido pyridine or derivatives thereof, and stirring at room temperature or heated and stirred reaction are spent the night;
(2) filtered by the mixture in step (1), low pressure concentrates, and obtains the solidliquid mixture of seldom amount, adds solvent, hold over night, obtain colourless bulk crystals, be presoma (I).
4. method as claimed in claim 3, wherein, the temperature of cold condition and/or cryopreservation be-78 DEG C to 0 DEG C, and use is selected from liquid nitrogen, dry ice, liquefied ammonia, any one cooling way of cold cycle pump and combination thereof.
5. method as claimed in claim 3, wherein, the time of stirring at room temperature or heated and stirred is 1 to 10 hour.
6. method as claimed in claim 3, wherein, the temperature of stirring at room temperature or heated and stirred is 25 DEG C to 150 DEG C.
7. method as claimed in claim 3, wherein, the molar ratio of the first reactant and the second reactant is 1.0:1.0 to 1.0:3.0.
8. method as claimed in claim 3, wherein, solvent is selected from any one and combination thereof of following organic solvent: be selected from C
5h
12~ C
8h
18straight or branched alkane, C
5h
10~ C
8h
16the alkane of cyclic alkane; Be selected from the aromatic hydrocarbon of benzene, toluene; Be selected from the ethers of ether, tetrahydrofuran (THF).
9. method as claimed in claim 3, wherein, the condition of reaction mixture filtering and concentrating is: concentrated 25 ~ 80 DEG C of pressurizations, pressure is 0.05 ~ 0.20MPa.
10. a method, semi-conductor device manufacturing method, comprise and adopt the film of CVD or ALD technique preparation containing aluminium element, described film adopts aluminium presoma as claimed in claim 1 manufacture, wherein, described film comprises aluminum metal film, the sull containing aluminium, the nitride film containing aluminium, any one and combination containing the alloy firm of aluminium.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998036035A1 (en) * | 1997-02-13 | 1998-08-20 | Queen's University At Kingston | Luminescent compounds and methods of making and using same |
| CN1461779A (en) * | 2002-04-19 | 2003-12-17 | 捷时雅株式会社 | Substance for forming electrically-conducting film and electrically-conducting film and its manufacturing method |
| WO2007136184A1 (en) * | 2006-05-18 | 2007-11-29 | Dnf Co., Ltd. | Aluminum compound for forming aluminum films by chemical vapor deposition and their synthesis |
| CN103531658A (en) * | 2013-09-25 | 2014-01-22 | 北京七星华创电子股份有限公司 | Atomic layer deposition preparation method for aluminum oxide thin film |
-
2015
- 2015-02-09 CN CN201510067153.2A patent/CN104557999B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998036035A1 (en) * | 1997-02-13 | 1998-08-20 | Queen's University At Kingston | Luminescent compounds and methods of making and using same |
| CN1461779A (en) * | 2002-04-19 | 2003-12-17 | 捷时雅株式会社 | Substance for forming electrically-conducting film and electrically-conducting film and its manufacturing method |
| WO2007136184A1 (en) * | 2006-05-18 | 2007-11-29 | Dnf Co., Ltd. | Aluminum compound for forming aluminum films by chemical vapor deposition and their synthesis |
| CN103531658A (en) * | 2013-09-25 | 2014-01-22 | 北京七星华创电子股份有限公司 | Atomic layer deposition preparation method for aluminum oxide thin film |
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