KR20150054200A - Germanium-tellurium single precursors, preparation method thereof and process for the formation of thin films using the same - Google Patents
Germanium-tellurium single precursors, preparation method thereof and process for the formation of thin films using the same Download PDFInfo
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- KR20150054200A KR20150054200A KR1020130136363A KR20130136363A KR20150054200A KR 20150054200 A KR20150054200 A KR 20150054200A KR 1020130136363 A KR1020130136363 A KR 1020130136363A KR 20130136363 A KR20130136363 A KR 20130136363A KR 20150054200 A KR20150054200 A KR 20150054200A
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- germanium
- tellurium
- single precursor
- formula
- thin film
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- VDDXNVZUVZULMR-UHFFFAOYSA-N germanium tellurium Chemical compound [Ge].[Te] VDDXNVZUVZULMR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002243 precursor Substances 0.000 title claims abstract description 31
- 239000010409 thin film Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 abstract description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002159 nanocrystal Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910000618 GeSbTe Inorganic materials 0.000 description 3
- 229910005900 GeTe Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
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Classifications
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- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention relates to a germanium-tellurium single precursor represented by the following general formula (1), wherein the germanium-tellurium single precursor has an improved thermal stability and volatility and has an advantage of not requiring additional tellurium during the manufacture of the thin film So that a thin film containing germanium-tellurium of high quality can be formed.
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group.
Description
The present invention relates to a novel germanium-tellurium single precursor, a germanium-tellurium single precursor capable of producing a germanium tellurium thin film of good quality, a process for producing the germanium-tellurium single precursor and a process for producing a germanium- ≪ / RTI >
Phase-change materials are substances that have different states of crystalline and amorphous states depending on the 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.
A variety of phase change materials that can be applied to memory devices are currently known. Among them, GST (GeSbTe) based alloys are typically used. For the production of such GST alloys, European Journal of Inorganic Chemistry; 2009; Chen et al. Have studied the germanium tellurium precursor and its preparation method. However, the germanium tellurium precursor of the above literature has a problem in improving the performance of the PRAM at present, and the thermal stability, the chemical reactivity, the volatility and the germanium tellurium metal It is urgently required to improve the deposition rate.
DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel germanium-tellurium single precursor which can improve the thermal stability and volatility and can easily produce a thin film containing high quality germanium-tellurium at a low temperature .
In order to achieve the above object, the present invention provides a germanium-tellurium single precursor represented by the following general formula (1).
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group.
The present invention also provides a method for preparing a germanium-tellurium single precursor represented by Formula 1, which comprises reacting a Te powder with a compound represented by Formula 2 below.
(2)
R 1 R 2 GeX 2
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group, and X is any one of Cl, Br and I.
The present invention also provides a method for growing a germanium-tellurium-containing thin film using the germanium-tellurium single precursor of Formula 1 above.
The germanium-tellurium single precursor represented by the general formula (1) of the present invention has improved thermal stability and volatility and has an advantage of not requiring addition of tellurium during the production of a thin film. Therefore, it is possible to easily produce germanium- Can be produced.
1 is a 1 H NMR spectrum for Example 1. Fig.
2 is an X-ray crystal structure for Example 1. Fig.
FIG. 3 is an XRD pattern of nanocrystals obtained by pyrolyzing Ge 3 Te 3 Et 6 (i) and Ge 3 Te 3 Bu 6 (ii) prepared in Examples 1 and 2.
4 is a SEM photograph of nanocrystals obtained by pyrolyzing Ge 3 Te 3 Et 6 .
5 is a SEM photograph of nanocrystals obtained by pyrolyzing Ge 3 Te 3 Bu 6 .
6 is an EDS of nanocrystals obtained by pyrolyzing Ge 3 Te 3 Et 6 and Ge 3 Te 3 Bu 6 .
7 is XPS of nanocrystals obtained by pyrolyzing Ge 3 Te 3 Et 6 and Ge 3 Te 3 Bu 6 .
The present invention relates to a germanium-tellurium single precursor represented by the following general formula (1)
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group.
In the above formula (1), it is preferable that R 1 is independently selected from CH 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 .
The germanium-tellurium single precursor represented by Formula 1 according to the present invention can be prepared by reacting a compound represented by Formula 2 as a starting material with Te powder in a solvent of THF or toluene to induce a substitution reaction.
(2)
R 1 R 2 GeX 2
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group, and X is any one of Cl, Br and I.
In
The solvent is not particularly limited, but a THF solution or toluene can be preferably used.
A specific reaction process for preparing the germanium-tellurium single 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-tellurium single precursor represented by the above formula (1) is a stable liquid at room temperature and is thermally stable and has good volatility.
The novel germanium-tellurium single precursor of the present invention can be advantageously applied to processes 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
germanium- Tellurium Synthesis of single precursor materials
Example One: Ge 3 Te 3 Meat 6 Manufacturing
To a 125 mL Schlenk flask, 1 g (8 mmol) of tellurium (Te) powder was added to 16 mL of 1 M Li (BEt 3 H) THF solution and 20 mL of THF and stirred for 5 minutes. Te powder reacted to form a purple solution Was created. Then, 8 mmol of Et 2 GeCl 2 was dissolved in 5 mL of THF, and the solution was added to the above-prepared Li 2 Te solution, and the solution turned yellow. After the reaction for 45 minutes, THF was removed and 100 mL of hexane was added. The LiCl was again filtered off and the solvent was removed to obtain a liquid product (0.7 g, yield: 35%).
1 H-NMR of the obtained compound is shown in Fig.
Elemental analysis Calcd for Ge 3 Te 3 Et 6 (%): C, 18.60; H, 3.91.
Found (%): C, 18.69; H, 3.90.
1 H-NMR (400 MHz, CDCl 3 ):? 1.10 (3H, CH 3 , t), 1.58 (2H, CH 2 , quad.).
Example 2: Ge 3 Te 3 This 6 Manufacturing
Except that the same mole of Bu 2 GeCl 2 was used instead of Et 2 GeCl 2 of Example 1, all the remaining reactions being the same. The product is a brown liquid. (1 g, 40% yield)
Elemental analysis Calcd for Ge 3 Te 3 Bu 6 (%): C, 30.55; H, 5.77.
Found (%): C, 30.45; H, 5.73.
1 H-NMR (400 MHz, CDCl 3): δ0.91 (3H,
1.60 (2H, CH 2, quad ).
germanium- Tellurium Analysis of single precursor materials
In order to confirm the specific structure of the germanium-tellurium single precursor compound synthesized in Example 1, a single crystal was obtained by slightly lowering the temperature, and a crystal structure (X-ray structure) was obtained using a Bruker SMART APEX II X-ray Diffractometer The results are shown in Fig. Through this, the structure of the germanium-tellurium single precursor of the present invention can be confirmed.
germanium- Tellurium Synthesis and analysis of nanocrystals using single precursor
First, 30 mL of oleylamine was heated to 90 ° C. and maintained at a vacuum for 1 hour, and then the temperature was raised to 300 ° C. while blowing nitrogen. To this was added 0.15 g of the germanium-tellurium single precursor compound synthesized in Example 1, and heating was continued. After about 1 hour and a half, the color of the solution began to become darker. The solution was heated for 2 hours, 4 hours, and 6 hours, respectively. After cooling, the GeTe nanocrystals were washed, dried in vacuum and dispersed in hexane to synthesize nanocrystals.
The XRD pattern of the crystals produced is shown in Fig. It is confirmed that this is completely consistent with GeTe.
The nanocrystals prepared above were observed with an electron microscope (TEM) and are shown in FIGS. 4 and 5. FIG. FIG. 4 is a photograph of a nanocrystal of Ge 3 Te 3 Et 6 , which confirms the determination of an octahedron structure. FIG. 5 is a photograph of a nanocrystal of Ge 3 Te 3 Bu 6 , Can be confirmed. The size of the crystals is about 1 μm and nanocrystals of uniform size and shape are produced with relatively uniform and smooth surfaces.
As shown in FIG. 6, EDX analysis was carried out to confirm that all the nanocrystals had a composition of Ge: Te of 1: 1. As shown in FIG. 7, it was confirmed that the synthesized nanocrystals were also GeTe in the XPS analysis.
Claims (5)
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group.
Wherein R 1 and R 2 are independently from each other selected from CH 3 , C 2 H 5 , CH (CH 3 ) 2 and C (CH 3 ) 3 .
(2)
R 1 R 2 GeX 2
Wherein R 1 and R 2 are each independently a C1-C10 linear or branched alkyl group, and X is any one of Cl, Br and I.
Wherein the thin film growth process is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
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| KR1020130136363A KR20150054200A (en) | 2013-11-11 | 2013-11-11 | Germanium-tellurium single precursors, preparation method thereof and process for the formation of thin films using the same |
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| KR1020130136363A KR20150054200A (en) | 2013-11-11 | 2013-11-11 | Germanium-tellurium single precursors, preparation method thereof and process for the formation of thin films using the same |
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| KR20150054200A true KR20150054200A (en) | 2015-05-20 |
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| KR1020130136363A KR20150054200A (en) | 2013-11-11 | 2013-11-11 | Germanium-tellurium single precursors, preparation method thereof and process for the formation of thin films using the same |
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2013
- 2013-11-11 KR KR1020130136363A patent/KR20150054200A/en not_active Application Discontinuation
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