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Solution raw material for organic metal chemical vapor deposition and complex oxide dielectric thin film formed by using such raw mataerial

A chemical vapor deposition and organometallic technology, which is applied in metal material coating process, gaseous chemical plating, circuit, etc., can solve problems such as troublesome film preparation, reduced film forming stability, and unstable coordination compounds, etc., and achieves excellent results. Effects of Gradient Coverage and High Film Formation Properties

Inactive Publication Date: 2007-07-18
MITSUBISHI MATERIALS CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to gasification, the Sr(dpm) of the solid raw material 2 and liquid L n The evaporation temperature varies greatly, L n Dissociation during heating may easily cause the phenomenon that the Sr raw material cannot be transported into the film-forming chamber
In addition, as the organic lead compound raw material, β-diketone compound, which is an organometallic compound, is different from other organometallic compounds in that turbidity and precipitation occur in polar solvents such as THF, so there is a problem that it causes trouble in thin film preparation.
Furthermore, THF is polymerizable, and if heated for vaporization, ring-opening polymerization occurs, and there is a problem that the coordination compound is easily unstable.
[0012] In addition, in the metal compound solution described in the above-mentioned Patent Document 2, although high film-forming speed and film-forming stability can be obtained by using cyclohexane as a solvent, due to the high melting point of this cyclohexane, the When the solution raw material obtained by dissolving an organometallic compound in cyclohexane is stored or transported in a storage container, etc., in a cold environment where the temperature is lower than that of the cyclohexane, the solution raw material in the storage container will freeze, generate particles, etc., and exist The problem of reduced film-forming stability

Method used

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  • Solution raw material for organic metal chemical vapor deposition and complex oxide dielectric thin film formed by using such raw mataerial
  • Solution raw material for organic metal chemical vapor deposition and complex oxide dielectric thin film formed by using such raw mataerial

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] First, prepare Pb(dpm) separately 2 As an organic Pb compound, Zr(dmhd) was prepared 4 As an organic Zr compound, Ti(O-i-Pr) was prepared 2 (dpm) 2 as an organic Ti compound. Wherein, dmhd represents 2,6-dimethyl-3,5-heptanedione residue, and O-i-Pr represents isopropoxide. The above Pb(dpm) 2 , Zr(dmhd) 4 and Ti(O-i-Pr) 2 (dpm) 2 mixed so that it forms the predetermined Pb 1.15 (Zr 0.45 Ti 0.55 )O 3 The composition ratios were dissolved in the organic solvents shown in Tables 1 to 3 below to prepare 0.3 mol / L solution raw materials No. 1 to No. 15-4, respectively. Also, prepare O 2 as an oxygen source.

[0051] Then, prepare Pt(200nm) / Ti(20nm) / SiO 2 A (500 nm) / Si substrate was used as a substrate, and this substrate was set in the film formation chamber of the MOCVD apparatus shown in FIG. 1 . In addition, the prepared solution raw material is stored in the raw material container 18 . Then, the temperature of the substrate 13 was set at 600° C., the tem...

comparative test 1

[0055] In order to confirm whether the PZT dielectric thin films obtained in Example 1 and Comparative Example 1 have high remnant polarization, the following remnant polarization measurement and gradient coating test were performed on these films. The results are shown in Tables 1 to 3, respectively.

[0056] (1) Determination of residual polarization

[0057] On the film-formed substrate, the upper electrode was formed of 200 nm of Pt, and the residual polarization of the PZT dielectric thin film was measured using a ferroelectric detector (Ferroelectric Testeichi) (manufactured by Rajendontechnorochi Co., Ltd.; RT6000S).

[0058] (2) Gradient coverage test

[0059] The gradient coverage of the PZT dielectric thin film on the film-formed substrate was measured from a cross-sectional SEM (Scanning Electron Microscope) image. The gradient coverage is represented by the numerical value of a / b when the thin film 20 is formed on the substrate 13 having steps such as grooves sho...

Embodiment 2

[0068] First, prepare Ba(dpm) separately 2 Prepare Sr(dpm) as an organic Ba compound 2 As an organic Sr compound, Ti(O-i-Pr) was prepared 2 (dpm) 2 as an organic Ti compound. Put the above Ba(dpm) 2 , Sr(dpm) 2 and Ti(O-i-Pr) 2 (dpm) 2 mixed to form a predetermined (Ba 0.7 St 0.3 )TiO 3 The composition ratios were dissolved in the organic solvents shown in Tables 4 to 6 below to prepare 0.3 mol / L solution raw materials No. 16 to No. 30-4, respectively. Also, prepare O 2 as an oxygen source.

[0069] Then, prepare Pt(200nm) / Ti(20nm) / SiO 2 A (500 nm) / Si substrate was used as a substrate, and this substrate was set in the film formation chamber of the MOCVD apparatus shown in FIG. 1 . In addition, the prepared solution raw material is stored in the raw material container 18 . Then, the temperature of the substrate 13 was set to 700° C., the temperature in the vaporization chamber 26 was set to 250° C., and the pressure in the film formation chamber 10 was set to abo...

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Abstract

Disclosed is a solution raw material for organic metal chemical vapor deposition having high film-forming characteristics and excellent step coverage. Also disclosed is a complex oxide dielectric thin film formed by using such a raw material. Specifically, an improved solution raw material for organic metal chemical vapor deposition obtained by dissolving one or more organic metal compounds in an organic solvent is disclosed which is characterized in that the organic solvent is 1,3-dioxolane or a mixed solvent obtained by mixing a first solvent composed of 1,3-dioxolane and a second solvent composed of one or more solvents selected from the group consisting of alcohols, alkanes, esters, aromatic series, alkyl ethers and ketones.

Description

technical field [0001] The present invention relates to a method for forming a DRAM (Dynamic Random Access Memory) or FRAM (ferroelectric random access memory) by an organic metal chemical vapor deposition method (Metal Organic Chemical Vapor Deposition, hereinafter referred to as MOCVD method). ) and other memory, and dielectric filters (inductor フイルタ一) and other composite oxide-based dielectric thin films for MOCVD solution raw materials and composite oxide-based dielectric thin films produced using the raw materials. Background technique [0002] Examples of such complex oxide-based dielectric thin films include lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), barium strontium titanate (BST), and the like. As the organometallic compound used as the raw material of the dielectric thin film, di-tert-valerylmethane ((CH) is generally used. 3 ) 3 CCOCH 2 COC(CH 3 ) 3 , hereinafter referred to as dpm) and other β-diketone compou...

Claims

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Application Information

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IPC IPC(8): C23C16/40H01L21/316
Inventor 柳泽明男斋笃曾山信幸
Owner MITSUBISHI MATERIALS CORP
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