CN112038214A - Zirconium oxide film and deposition method and application thereof - Google Patents
Zirconium oxide film and deposition method and application thereof Download PDFInfo
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- CN112038214A CN112038214A CN202010567101.2A CN202010567101A CN112038214A CN 112038214 A CN112038214 A CN 112038214A CN 202010567101 A CN202010567101 A CN 202010567101A CN 112038214 A CN112038214 A CN 112038214A
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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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
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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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02658—Pretreatments
Abstract
The invention relates to a zirconia film and a deposition method and application thereof. Zirconium oxide film ZrO2The deposition method of (1), comprising: the zirconia film was deposited by chemical vapor deposition and the deposition was preceded by the supply of a cyclopentyl methyl ether-based solvent prior to the supply of the zirconium source. The invention uses cyclopentyl methyl ether solvent as additive to promote the flow of zirconium source, and can avoid the problem of uneven film caused by local excessive deposition.
Description
Technical Field
The invention relates to the field of semiconductor preparation, in particular to a zirconium oxide film and a deposition method and application thereof.
Background
With the miniaturization of semiconductor devices, the difficulty of designing capacitors, which are one of the main structures of semiconductor devices, is increased, and particularly, the difficulty of improving capacitance is increased. Meanwhile, the step coverage rate of the dielectric film in the capacitor is insufficient, so that the electric field distribution is not uniform, and the difficulty in improving the capacitance is increased.
Disclosure of Invention
The invention aims to provide a method for depositing a zirconium oxide film, which utilizes a cyclopentyl methyl ether solvent as an additive to promote the flow of a zirconium source, can avoid the problem of uneven film caused by local excessive deposition and can improve the step coverage rate of the zirconium oxide film.
In order to achieve the above purpose, the invention provides the following technical scheme:
zirconium oxide film ZrO2The deposition method of (1), comprising: depositing a zirconium oxide film by using a chemical vapor deposition method and a monoatomic layer deposition method, and supplying a cyclopentyl methyl ether solvent before supplying a zirconium source during deposition;
the cyclopentyl methyl ether solvent is a hydrophobic ether solvent at least containing cyclopentyl.
The deposition method supplies the cyclopentyl methyl ether solvent before supplying the zirconium source, so that excessive deposition of the zirconium source in a local area (especially excessive deposition in the top area of a capacitor pattern) can be avoided, a zirconium oxide film with good uniformity is obtained, the step coverage rate is good, the electric field distribution of the capacitor is uniform, and the capacitance is favorably improved. The reason why the uniformity can be improved by adding the cyclopentyl methyl ether solvent is mainly as follows: on one hand, the cyclopentyl methyl ether solvent is used as a hydrophobic ether solvent, has high chemical stability at high temperature, does not undergo peroxidation or decomposition, has a proper boiling point (the boiling point of cyclopentyl methyl ether is 106 ℃), and can promote the flow of the zirconium source, so that the zirconium source is prevented from being accumulated at the top of the pattern to cause excessive deposition; on the other hand, the cyclopentyl methyl ether-based solvent has an effect of oxygen passivation, and thus can alleviate local excess zirconium oxidation.
The above deposition method is mainly used for the preparation of capacitors in semiconductors, but this does not limit the application scope of the present invention.
Semiconductor devices to which the present invention is applicable include, but are not limited to: DRAM, 2D NAND, 3D NAND, or LCD.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings.
FIG. 1 is a capacitor structure with a dielectric film having good step coverage;
FIG. 2 is a capacitor structure with a dielectric film having poor step coverage;
FIG. 3 is a topographical view of a prior art deposited zirconia film;
FIG. 4 is a topographical view of a deposited zirconia film of the present invention.
Figure 5 is a sequence of steps in the process of depositing a dielectric film according to the present invention;
FIG. 6 is a schematic view of the formation of a solvent layer on the surface of a support by the method of the present invention.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be understood that the description is illustrative only and is not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
Various structural schematics according to embodiments of the present disclosure are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, as actually required.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed.
Taking the capacitor structure shown in fig. 1 and 2 as an example, representing the step coverage in two different cases, the dielectric film 1 in fig. 1 has good step coverage, and the device formed by using the structure necessarily has uniform electric field distribution. On the other hand, the dielectric film 1 in fig. 2 has a poor step coverage, and the dielectric film thickness at the top is significantly larger than that at the bottom, so that the electric field distribution of the device formed by this structure is not uniform, resulting in poor electrical characteristics.
It follows that the step coverage of the dielectric film is critical to the capacitance and electrical properties of the semiconductor during the fabrication of the capacitor in the semiconductor.
The topography of the dielectric film obtained using conventional deposition methods is shown in fig. 3, with significantly more deposition on the top of the step than in other regions. To improve this phenomenon, the present invention proposes the following embodiments.
When the zirconium oxide film is deposited by using a chemical vapor deposition method, a cyclopentyl methyl ether solvent is supplied before a zirconium source is supplied; subsequent operations, such as supplying ozone or oxygen, and optionally purging, evacuating, etc., are then performed.
The cyclopentyl methyl ether-based solvent is supplied as a hydrophobic ether-based solvent containing at least a cyclopentyl group, and typically includes: cyclopentyl methyl ether or alkyl-substituted cyclopentyl methyl ether, and the like.
Because the cyclopentyl methyl ether solvent is used as a hydrophobic ether solvent, the chemical stability is high at high temperature, the peroxidation or the decomposition is avoided, and the boiling point is proper (the boiling point of the cyclopentyl methyl ether is 106 ℃), the flow of the zirconium source can be promoted, so that the excessive deposition caused by the accumulation of the zirconium source at the top of the pattern can be avoided, and other impurities can be avoided from being introduced; in addition, the cyclopentyl methyl ether solvent has the effect of oxygen passivation, thereby alleviating local excess zirconium oxidation.
The profile of the dielectric film obtained using the above method is shown in fig. 4. Compared with a deposition method without adding a cyclopentyl methyl ether solvent, the method can increase the capacitance of the DRAM from 7.5fF/cell to 8.3fF/cell, improve by more than 10 percent, and reduce the dielectric film leakage current (D0 fail bit) from 200bits/chip to less than 80bits/chip, and improve by more than 60 percent.
Fig. 4 merely illustrates that the electrode covered with the dielectric film is titanium nitride TiN, but the present invention also uses a covering of other electrodes, for example, nitrides of various metals (nickel nitride, vanadium nitride, etc.).
The above embodiment preferably uses a pulsed supply of the reaction source (zirconium source, reaction gas, etc.) in the following order for each cycle: supplying cyclopentyl methyl ether solvent, supplying zirconium source, purging reaction source, supplying reaction gas and purging reaction gas.
As shown in fig. 5, the dielectric film is deposited in the following order: oxygen passivation (02passivation), supplying a zirconium source, purging a reaction source, supplying a reaction gas and purging the reaction gas; oxygen passivation may be achieved by the method of the present invention by supplying a cyclopentyl methyl ether-based solvent, such as cyclopentyl methyl ether, having the formula:
in this method, a solvent layer is first formed on the surface of the support, as shown in fig. 6.
The supply of the cyclopentyl methyl ether solvent in the method is suitably carried out in an environment of 200 to 250 ℃.
The above embodiments do not limit the types of zirconium sources and reactants, and zirconium sources that may be used include, but are not limited to, one or more of the following: zr (DMA)2(Me)2，Zr(EMA)2(Me)2，Zr(DMA)(Me)2(Cp)，Zr(EMA)2(Cp)2，Zr(Cp)2(Me)2，Zr(Cp)(EMA)(Me)2；
Wherein the content of the first and second substances,
cp is a cyclopentadienyl group, and is a cyclopentadienyl group,
METHD is methoxy ethoxy tetramethyl heptanedionate,
MPD is 2-methyl-2, 4-pentyldioxy,
THD is 2,3,6, 6-tetramethyl-3, 5-heptanedionato,
EMA is ethyl methyl amino, and EMA is ethyl methyl amino,
DMA is a dimethylamino group,
me is methyl.
The reaction gas which can be used is oxygen, ozone, etc.
The cyclopentyl methyl ether-based solvent refers to a hydrophobic ether-based solvent containing at least a cyclopentyl group, such as a typical cyclopentyl methyl ether.
In addition, the method of the present invention is not limited by the equipment, and typical single-wafer type equipment, cluster type equipment, furnace type equipment or rotary type equipment (Merry-go-round) can be adopted.
The above method and the ZrO produced2The films may be used to make any type of semiconductor device, including but not limited to: DRAM, 2D NAND, 3D NAND, or LCD.
The chemical vapor deposition method of the present invention is a chemical vapor deposition method in a broad sense, i.e. a method of forming a film by chemical reaction of vapor phase reactants, including conventional CVD, ALD, etc.
In the above description, the technical details of patterning, etching, and the like of each layer are not described in detail. It will be appreciated by those skilled in the art that layers, regions, etc. of the desired shape may be formed by various technical means. In addition, in order to form the same structure, those skilled in the art can also design a method which is not exactly the same as the method described above. In addition, although the embodiments are described separately above, this does not mean that the measures in the embodiments cannot be used in advantageous combination.
The embodiments of the present disclosure have been described above. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The scope of the disclosure is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be devised by those skilled in the art without departing from the scope of the present disclosure, and such alternatives and modifications are intended to be within the scope of the present disclosure.
Claims (11)
1. A method for depositing a zirconia film, comprising: depositing a zirconium oxide film by chemical vapor deposition, and supplying a cyclopentyl methyl ether solvent before supplying a zirconium source during deposition;
the cyclopentyl methyl ether solvent is a hydrophobic ether solvent at least containing cyclopentyl.
2. A deposition method according to claim 1, wherein the cyclopentyl methyl ether-based solvent is cyclopentyl methyl ether.
3. A deposition method according to claim 1 or 2, characterized in that the zirconium source is selected from at least one of the following: zr (DMA)2(Me)2，Zr(EMA)2(Me)2，Zr(DMA)(Me)2(Cp)，Zr(EMA)2(Cp)2，Zr(Cp)2(Me)2，Zr(Cp)(EMA)(Me)2；
Wherein the content of the first and second substances,
cp is a cyclopentadienyl group, and is a cyclopentadienyl group,
METHD is methoxy ethoxy tetramethyl heptanedionate,
MPD is 2-methyl-2, 4-pentyldioxy,
THD is 2,3,6, 6-tetramethyl-3, 5-heptanedionato,
EMA is ethyl methyl amino, and EMA is ethyl methyl amino,
DMA is a dimethylamino group,
me is methyl.
4. The deposition method according to claim 1 or 2, wherein the supplying of the cyclopentyl methyl ether-based solvent is performed in an environment of 200 to 250 ℃.
5. A deposition method according to claim 1 or 2, wherein the zirconium source is supplied in pulses; further comprising, in order after supplying the zirconium source: purging a reaction source, supplying reaction gas and purging the reaction gas.
6. The deposition method according to claim 5, further comprising, in order after supplying the zirconium source: purging a reaction source, supplying reaction gas and purging the reaction gas.
7. The deposition method according to claim 1, wherein the apparatus used for deposition is: single wafer, cluster, furnace or rotary (Merry-go-round) equipment.
8. A method of forming a capacitor in a semiconductor comprising depositing a dielectric film, said dielectric film being obtained by the deposition method of any one of claims 1 to 7.
9. A zirconia film obtained by the deposition method of any one of claims 1 to 7.
10. Use of the deposition method according to any of claims 1 to 7 or the preparation method according to claim 6 for the preparation of a semiconductor device.
11. The use according to claim 10, wherein the semiconductor device is a DRAM, a 2D NAND, a 3D NAND or an LCD.
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| CN202010567101.2A CN112038214A (en) | 2020-06-19 | 2020-06-19 | Zirconium oxide film and deposition method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102446890A (en) * | 2010-09-27 | 2012-05-09 | 尔必达存储器株式会社 | Semiconductor device, method of manufacturing same and adsorption site blocking atomic layer deposition method |
| CN102712662A (en) * | 2009-08-14 | 2012-10-03 | 乔治洛德方法研究和开发液化空气有限公司 | Hafnium- and zirconium-containing precursors and methods of using the same |
| US20170040172A1 (en) * | 2015-08-04 | 2017-02-09 | Samsung Electronics Co., Ltd. | Methods of forming material layer |
| US20180122645A1 (en) * | 2016-10-28 | 2018-05-03 | Hansol Chemical Co., Ltd | Precursor for vapor deposition having excellent thermal stability and preparing method thereof |
| KR102095710B1 (en) * | 2019-11-05 | 2020-04-01 | 주식회사 유진테크 머티리얼즈 | Method of depositing thin films using protective material |
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- 2020-06-19 CN CN202010567101.2A patent/CN112038214A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712662A (en) * | 2009-08-14 | 2012-10-03 | 乔治洛德方法研究和开发液化空气有限公司 | Hafnium- and zirconium-containing precursors and methods of using the same |
| CN102446890A (en) * | 2010-09-27 | 2012-05-09 | 尔必达存储器株式会社 | Semiconductor device, method of manufacturing same and adsorption site blocking atomic layer deposition method |
| US20170040172A1 (en) * | 2015-08-04 | 2017-02-09 | Samsung Electronics Co., Ltd. | Methods of forming material layer |
| US20180122645A1 (en) * | 2016-10-28 | 2018-05-03 | Hansol Chemical Co., Ltd | Precursor for vapor deposition having excellent thermal stability and preparing method thereof |
| KR102095710B1 (en) * | 2019-11-05 | 2020-04-01 | 주식회사 유진테크 머티리얼즈 | Method of depositing thin films using protective material |
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