KR101472473B1 - Germanium precursors with aminothiolate, preparation method thereof and process for the formation of thin films using the same - Google Patents
Germanium precursors with aminothiolate, preparation method thereof and process for the formation of thin films using the same Download PDFInfo
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- KR101472473B1 KR101472473B1 KR20120136556A KR20120136556A KR101472473B1 KR 101472473 B1 KR101472473 B1 KR 101472473B1 KR 20120136556 A KR20120136556 A KR 20120136556A KR 20120136556 A KR20120136556 A KR 20120136556A KR 101472473 B1 KR101472473 B1 KR 101472473B1
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- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 30
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 7
- 102000014961 Protein Precursors Human genes 0.000 title description 2
- 108010078762 Protein Precursors Proteins 0.000 title description 2
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000002360 preparation method Methods 0.000 title description 2
- 238000005755 formation reaction Methods 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 14
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 4
- 238000007792 addition Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 229910005829 GeS Inorganic materials 0.000 description 3
- 238000010928 TGA analysis Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910000618 GeSbTe Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000003287 optical Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UQMCSSLUTFUDSN-UHFFFAOYSA-N sulfanylidenegermane Chemical compound [GeH2]=S UQMCSSLUTFUDSN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RTIAWKZWXRELMB-UHFFFAOYSA-M CN(CC(C)([S-])C)C Chemical compound CN(CC(C)([S-])C)C RTIAWKZWXRELMB-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 206010057190 Respiratory tract infection Diseases 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N aminothiourea Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 antimony germanium Chemical compound 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Inorganic materials [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
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Abstract
The present invention relates to a germanium precursor represented by the following general formula (1), wherein the germanium precursor is a precursor containing sulfur and has the advantage of not requiring addition of sulfur during the production of the thin film, and has improved thermal stability and volatility, Germanium thin film can be formed.
[Chemical Formula 1]
Wherein R1 and R2 are each independently a C1-C10 linear or branched alkyl group, R3 and R4 are each independently a C1-C10 linear or branched alkyl or fluoroalkyl group, n is an integer from 1 to 3 Is selected from the number between.
Description
The present invention relates to a novel germanium precursor, and more specifically, to a germanium precursor capable of easily producing a high quality germanium sulfide thin film at a low temperature with improved thermal stability and volatility, a method for producing the germanium precursor, and a germanium sulfide thin film .
A phase change material is moved to a memory element of a nonvolatile memory device, which is a material having a different state in a crystalline state and an amorphous state depending on a temperature. Crystalline states exhibit lower resistivity than amorphous states and have ordered, ordered atomic arrangements. The crystalline state and the amorphous state are mutually reversible. That is, the crystalline state can be changed from the amorphous state to the amorphous state, and the amorphous state can be changed to the crystalline state again. A phase-change memory device (PRAM) is a memory device in which a mutually changeable state and a resistance value that can be clearly distinguished are applied to a memory device.
A typical form of PRAM has a phase change film electrically connected to a source or drain region of a transistor through a contact plug. The operation as the memory is performed by using the resistance difference due to the crystal structure change of the phase change film. That is, after the crystal structure of the phase change film is intentionally changed to the crystalline state or the amorphous state by appropriately changing the applied current, the resistance value according to the change of the crystalline state and the amorphous state is changed, so that the stored previous data value can be distinguished will be.
Various types of phase change materials that can be applied to memory devices are known, among which GST (GeSbTe) based alloys are typically used. In particular, for materials for germanium sulphide (GeS x ), for example, Optical Materials 29 (2007) 1344 1347 (CC Huang, K. Knight, DW Hewak; 30 August 2006) describe antimony germanium It has been disclosed that amorphous sulfide thin films are directly manufactured on silicon and commercial glass substrates. Through the analysis of such amorphous thin films, it has been disclosed that the composition of SB-GE-S is variously changed depending on the deposition temperature, and Electrochemical Deposition (Germanium sulphide) (GeS x ) in room temperature-electric ionic liquids (Langmuir; Sankaran Murugesan, Patrick Kearns, and Keith J. Stevenson; March 13, 2012) As a process, the development of the use of ionic liquids as electrolytes and the development of electrodeposited germanium sulfides by X-ray spectroscopy (SEM-EDS), Raman and X- It appears to be searched by electron spectroscopy (XPS).
However, since the process of depositing the germanium sulfide thin film induces the process of depositing Ge and S together according to the structure of the germanium precursor, a new germanium sulfide (GeS x ) improved in thermal stability, chemical reactivity, volatility, Development of precursors is urgently required.
It is an object of the present invention to provide a novel germanium precursor which can improve the thermal stability and volatility and can easily produce a high quality germanium sulfide thin film at a low temperature.
In order to achieve the above object, the present invention provides a germanium precursor represented by the following general formula (1).
[Chemical Formula 1]
Wherein R1 and R2 are each independently a C1-C10 linear or branched alkyl group, R3 and R4 are each independently a C1-C10 linear or branched alkyl or fluoroalkyl group, n is an integer from 1 to 3 Is selected from the number between.
The present invention also provides a method for preparing a germanium precursor represented by Formula 1, which comprises reacting a compound represented by
(2)
(Wherein, M represents the like Li, Na, K, NH 4 , R1, R2 are each independently a C1-C10, linear or branched alkyl group, R3, R4 are each independently a C1-C10 linear or branched, Alkyl or fluoroalkyl group, and n is selected from a number between 1 and 3.)
(3)
GeX 2
(Wherein X is Cl, Br, I, etc.).
The present invention also provides a method for growing a germanium sulfide thin film using the germanium precursor of Formula 1.
The germanium precursor represented by formula (1) of the present invention is a precursor containing sulfur and has improved thermal stability and volatility and has an advantage of not requiring addition of sulfur during the production of the thin film. Therefore, it is easy to use the germanium precursor as a precursor of high quality germanium sulfide Can be manufactured.
Figure 1 is a 1 H NMR spectrum for Ge (dmampS) 2 .
Figure 2 is a 13 C NMR spectrum for Ge (dmampS) 2 .
3 is an FT-IR spectrum for Ge (dmampS) 2 .
Figure 4 is TG / DTA data for Ge (dmampS) 2 .
5 is an X-ray crystal structure for Ge (dmampS) 2 .
The present invention relates to a germanium precursor represented by the following general formula (1)
[Chemical Formula 1]
Wherein R1 and R2 are each independently a C1-C10 linear or branched alkyl group, R3 and R4 are each independently a C1-C10 linear or branched alkyl or fluoroalkyl group, n is an integer from 1 to 3 Is selected from the number between.
Of R1 to R4 is in the above-mentioned formula (I), selected from linear or branched alkyl group of C1-C10, R1, R2 are independently CH 3, C 2 H 5, CH (CH 3) 2 and C (CH 3) with each other 3 and R 3 and R 4 are independently selected from CH 3 , CF 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 .
The germanium precursor represented by Formula 1 according to the present invention may be represented more specifically by a general formula Ge (daat) 2 (daat = dialkylaminoalkylthiolate), and the compound may be a compound (M daat) and a compound represented by the general formula (3) in a toluene solvent to induce a substitution reaction. More specific examples of the daat include 1- (dimethylamino) -2-methylpropane-2-thiolate, that is, dmampS.
(2)
(Wherein, M is such as Li, Na, K, NH 4 , R1, R2 are each independently C1-C10 linear or branched alkyl group, R3, R4 are each independently a C1-C10 linear or branched, N is an integer from 1 to 3. < RTI ID = 0.0 >
(3)
GeX 2
(Wherein X is Cl, Br, I, etc.).
Of R1 to R4 are according to the formula (2) selected from a linear or branched alkyl group of C1-C10, R1, R2 are independently CH 3, C 2 H 5, CH (CH 3) 2 and C (CH 3) with each other 3 and R 3 and R 4 are independently selected from CH 3 , CF 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 .
Toluene is preferably used as the solvent.
A specific reaction process for preparing the germanium precursor of the present invention can be represented by the following reaction formula (1).
[Reaction Scheme 1]
According to
The reactants in this reaction are used in stoichiometric equivalents.
The novel germanium precursor represented by the general formula (1) is a yellow solid which is stable at room temperature and is thermally stable and has good volatility.
When the germanium sulfide thin film is grown using the germanium precursor, there is an advantage that no additional sulfur is added during the thin film manufacturing process.
The novel germanium precursor of the present invention is preferably used as a precursor for the production of germanium sulfide thin film by a process using chemical vapor deposition (CVD) or atomic layer deposition (ALD).
The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.
Example
Synthesis of germanium precursor material
Example 1: Preparation of Ge (dmampS) 2
After dissolving GeCl 2 · dioxane (0.83 g, 3.59 mmol, 1 eq) and Li (dmampS) (1 g, 7.18 mmol, 2eq) in toluene (50 mL) in a 125 mL Schlenk flask, the reaction was allowed to proceed at room temperature for 15 hours . The mixture was filtered, and the solvent was removed under reduced pressure to obtain a yellow solid compound. The obtained compound was sublimed at 60 DEG C and 10 -2 torr to obtain white crystals (0.9 g, yield: 75%).
1 H-NMR, 13 C-NMR and FT-IR data of the obtained compound are shown in FIGS. 1 to 3.
1 H NMR (C 6 D 6 , 300.13MHz): δ 1.52 (s, 6H), 2.25 (s, 6H), 2.36 (s, 2H)
13 C NMR (C 6 D 6 , 75.04 MHz): δ 15.6, 35.3, 47.5, 66.9, 72.0.
Elemental Analysis for C 12 H 28 GeN 2 S 2 Calcd. (Found): C, 42.75 (41.13); H, 8.37 (8.34); N, 8.31 (8.08); S, 19.02 (19.70)
FT-IR (KBr, cm -1 ):? MS 416
In addition, thermogravimetric analysis (TGA) was used to measure the thermal stability, volatility and decomposition temperature of Ge (dmampS) 2 . In the TGA method, argon gas was introduced at a pressure of 1.5 bar / min while heating the product to 900 ° C at a rate of 10 ° C / minute. A TG / DTA graph of the germanium precursor compound synthesized in Example 1 is shown in Fig. In the germanium precursor compound obtained in Example 1, mass reduction was observed in two steps from around 190 ° C, and the final amount of the germanium precursor compound was observed to be 19%.
Claims (5)
[Chemical Formula 1]
Wherein R 1 and R 2 are independently selected from CH 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 , and R 3 and R 4 independently of one another are CH 3 , CF 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 , and n is selected from a number from 1 to 3.)
(2)
Wherein M is Li, Na, K or NH 4 and R 1 and R 2 are independently selected from CH 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 , R 3 and R 4 are independently selected from CH 3 , CF 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 and n is selected from a number from 1 to 3.
(3)
GeX 2
(Wherein X is Cl, Br or I).
Wherein the thin film growth process is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120136556A KR101472473B1 (en) | 2012-11-28 | Germanium precursors with aminothiolate, preparation method thereof and process for the formation of thin films using the same | |
| PCT/KR2013/003879 WO2013165221A1 (en) | 2012-05-04 | 2013-05-03 | Metal precursor using aminothiolate ligand, method for preparing same, and method for manufacturing thin film by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120136556A KR101472473B1 (en) | 2012-11-28 | Germanium precursors with aminothiolate, preparation method thereof and process for the formation of thin films using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140068718A KR20140068718A (en) | 2014-06-09 |
| KR101472473B1 true KR101472473B1 (en) | 2014-12-12 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101124226B1 (en) | 2011-02-15 | 2012-03-27 | 한국화학연구원 | Fabrication method of cis thin film using precursor |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101124226B1 (en) | 2011-02-15 | 2012-03-27 | 한국화학연구원 | Fabrication method of cis thin film using precursor |
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