KR100611730B1 - Precursors for preparing the pure silver thin-film in the chemical vapor deposition method and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a silver (Ag) monovalent precursor that can be usefully used in the production of high purity silver (Ag) thin film by chemical vapor deposition, and a method for preparing the same, wherein the precursor according to the present invention is represented by the following formula (1) Liquid organic silver having improved volatility and deposition properties by introducing betadiketones or betaketoester ligands and coordinating phosphite with a neutral ligand capable of providing a lone pair of electrons to a central silver (Ag) monovalent group. Ag) monovalent compound. Through chemical vapor deposition using the same, a high purity, high quality silver (Ag) thin film can be manufactured.

[Formula 1]

Wherein R is hydrogen, an alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Is any one selected from the group consisting of alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, Any one selected from the group consisting of an alkyl group, an alkoxy group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, L is a force Pit groups [P (OR2) 3, R2 in the group consisting of alkyl groups, benzyl, methyl fluoro, ethyl fluoride, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Which one is selected.)

Description

Precursors for preparing the pure silver thin-film in the chemical vapor deposition method and manufacturing method

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a chemical vapor deposition reaction apparatus for thin film production.

The present invention relates to a silver (Ag) monovalent precursor that can be usefully used in producing a high purity silver (Ag) thin film by chemical vapor deposition (Chemical Vapor Deposition) and a method for producing the same.

In recent years, attention has been focused on high-purity silver (Ag) thin films as well as on silver-based materials, enabling finer patterns to be produced than conventional thin-film pastes. Studies on the manufacture of thin films using chemical vapor deposition have been started.

Silver (Ag) thin films are applied to various technical fields. Representative examples include the application of silver to solar cells to increase cell efficiency, sterilization coating materials, and additives to increase the critical temperature (high-Tc) of superconductors. Practical application and feasibility experiments are underway. With the increasing density of semiconductor integrated circuits in today's microelectronics, wiring also requires low electrical resistance, high melting point, and thin line width wiring material for high density integrated circuits.

Aluminum is being used as an interconnect material, and research is being conducted to replace copper having a low resistivity value (2.66 μm cm) with 1.67 μm cm. However, silver (Ag) has the lowest resistivity value (1.62μΩ㎝) among the existing materials in nature and its melting point (962 ℃) is about 100 ℃ lower than copper, but it is lower than aluminum (660 ℃). It is expected to have a high potential of application as a new wiring material for the microelectronics industry because the electron migration resistance is higher than aluminum because it has a value of about 300 ° C.

However, despite the excellent electrical conductivity of silver (Ag), when the conventional silver (I) precursor is applied to the chemical vapor deposition method, the volatility is lower than that of the copper (I) precursor, low thermal stability at room temperature, and high substrate deposition. Several drawbacks such as temperature remain a challenge.

Meanwhile, various studies are underway on precursors, which are the most important raw materials in the silver (Ag) thin film manufacturing process using chemical vapor deposition.

In 1990 US Patent 4,948,623, DB Beach et al. Inventors described M (C ₅ H ₅ )... A new silver (Ag) precursor, such as P (C ₂ H ₅ ) ₃ (where M = Cu ₊₁ , Ag ₊₁ , Au ₊₁ ), was reported.

However, in the case of monovalent copper, the deposition temperature of silver (Ag) was relatively high at 300 ° C., and the decomposition temperature was also high at 500 ° C. In addition, silver (Ag) precursors reported very low volatility. On the other hand, the precursor synthesized for the production of silver (Ag) thin film can be generally expressed as XAgL (X = negative ligand, L = negative ligand), beta which is used as a ligand of the most common organometallic compound precursor In the case of diketone (β-diketone), most of the divalent ions have low vapor pressure characteristics due to silver (Ag) properties, and only 1,1,1,5,5,5-hexafluoro-2,4-pentanedione Research has been limited to (1,1,1,5,5,5-hexafluorofluoro-2,4-pentanedione), but even in this case, there is a problem in that fluorine contained in the ligand as an impurity is contained in the thin film. have.

And Inorg. Chemi. Acta vol. In 328, 134-146, and 2002, DAEdwards et al. (3) proposed a silver precursor using a variety of carboxylic acids as ligands, which reported that the precursor was not fully decomposed during deposition and low vapor pressure. However, there are still problems such as high deposition rate, high resistance value of the thin film due to impurities.

Even for neutral ligands, many [(β-diketonato) Ag (alkene or alkyne)] materials that mimic copper precursors to which various alkenes or alkyls having pi bonding ability are applied have been known, but silver (Ag) precursors are copper precursors. Unlike the low volatility, heat and light instability, there are many disadvantages in the application of chemical vapor deposition. In particular, precursor materials containing alkenes have the disadvantage of decomposing during vaporization prior to deposition in the substrate.

In addition, in order to solve the problems of the aforementioned fluorine-containing precursors, research on the synthesis of precursors containing no fluorine is underway. However, in the case of precursors that do not contain fluorine, silver (Ag) ions are easily reduced by light. For recently N.H. Dryden and two other researchers found Chem. Mater. vol. 5, 765-766, 1993 and in D.A. Edwards and three others are Inorg. Chemie Acta. For coordinating alkenes or alkyne neutral ligands in vol. 328, 134-146, 2002, we report precursors coordinated with phosphine ligands in order to solve the stability problems of precursors raised during the chemical vapor deposition process.

However, these precursors are formed in solid form to ensure the stability of the precursor, but the problem of corroding the inside of the reactor due to inferior volatility, which is an essential requirement of the precursor, and flammability and corrosiveness of the ligand, remains a challenge.

Accordingly, the present inventors have made up for the shortcomings of the thermal stability of the silver (Ag) precursor, including a minimal fluorine group, and having a low pyrolysis temperature, in particular, to synthesize a liquid volatile (Ag) monovalent precursor having high volatility. The valent silver nitrate can provide a non-covalent electron pair to a silver monovalent compound synthesized by a metal substitution reaction with sodium beta diketonate [Na (β-diketonate)] or sodium betaketoester [Na (β-ketoester)]. The present invention has been accomplished by introducing phosphite into a neutral ligand, which can synthesize a liquid volatile silver (Ag) monovalent precursor.

Accordingly, an object of the present invention is to provide a silver (Ag) monovalent compound precursor useful in the production of high purity silver (Ag) thin film by chemical vapor deposition using a liquid precursor having high volatility.

Another object of the present invention is to provide a method for producing the precursor.

In order to achieve the above object, the present invention provides a silver (Ag) monovalent precursor for producing a silver thin film by the chemical vapor deposition method represented by the formula (1).

Wherein R is hydrogen, an alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Is any one selected from the group consisting of alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, Any one selected from the group consisting of an alkyl group, an alkoxy group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, L is a force Pit groups [P (OR2) 3, R2 in the group consisting of alkyl groups, benzyl, methyl fluoro, ethyl fluoride, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Which one is selected.)

The precursor according to the present invention is a neutral ligand capable of introducing a beta-diketone or a beta-ketoester ligand and providing a non-covalent electron pair to silver (Ag) monovalent phosphite It is characterized by having a structure in which (phosphite) is coordinated.

In the precursor according to the present invention as described above, the alkyl group of R, R1, A and R2 is preferably any one selected from the group consisting of methyl, ethyl, normal propyl, isopropyl, and butyl.

In order to achieve the above-mentioned other object, the present invention

Monovalent silver nitrate and sodium betadiketonate [Na (β-diketonate)] or sodium betaketoester [Na] coordinated with phosphite [P (OR2) 3, R2 is alkyl group] as a neutral ligand capable of providing a lone pair (β-ketoester)] provides a method for preparing a silver (Ag) monovalent precursor represented by the following Chemical Formula 1, which is prepared by a metal substitution reaction by stirring for 2 to 5 hours.

[Formula 1]

Wherein R is hydrogen, an alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Is any one selected from the group consisting of alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, Any one selected from the group consisting of an alkyl group, an alkoxy group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, L is a force Pit groups [P (OR2) 3, R2 in the group consisting of alkyl groups, benzyl, methyl fluoro, ethyl fluoride, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Which one is selected.)

In the precursor preparation method according to the present invention as described above, the alkyl group of R, R1, A and R2 is preferably any one selected from the group consisting of methyl, ethyl, normal propyl, isopropyl and butyl.

In the precursor preparation method according to the present invention as described above, it is preferable that the metal substitution reaction is carried out under an ether or tetrahydrofuran solvent at 0 ℃.

In the method of preparing a precursor according to the present invention as described above, the monovalent silver nitrate in which phosphite [P (OR 2) ₃ , R 2 is an alkyl group] is coordinated with a neutral ligand capable of providing the unshared electron pair is the phosphite [P]. (OR2) ₃ , R2 may be prepared by mixing anhydrous silver nitrate with a mixed solution of an alkyl group] and diethyl ether by stirring until it becomes a non-colored liquid state.

In the precursor preparation method according to the present invention as described above, the sodium beta diketonate is metal sodium in pentane or diethyl ether and cooled to 0 ℃ condition and then excess beta diketonate is added to the metal sodium It can be prepared by stirring until all the reaction.

In the precursor preparation method according to the present invention as described above, the sodium betaketoester is metal sodium in pentane or diethyl ether and cooled to 0 ℃ condition and then excess beta ketoester is added to the metal sodium all reaction It can be prepared by stirring until it.

Hereinafter, the present invention will be described in more detail.

First, a method of preparing the precursor represented by Chemical Formula 1 according to the present invention will be described.

The precursor may be prepared by the following Schemes 1, 2, and 3.

Scheme 1

Sodium Betadiketonate or Sodium Betataketoester Synthesis

①β-diketone + Na → Na (β-diketonate) + H ₂

Reaction temperature 0 ℃ / Solvent (pentane or ether)

②β-ketoester + Na → Na (β-ketoester) + H ₂

Reaction temperature 0 ℃ / Solvent (pentane or ether)

The reaction scheme 1 is described in detail as follows.

30 ml of pentane or diethyl ether was added to a 100 ml shrink flask, followed by 0.2 mol of metallic sodium, followed by cooling to 0 ° C. When beta-diketone or beta-ketone ester is added slightly in excess of the equivalent (0.21 mol), hydrogen gas is generated and a white precipitate is formed slowly. After stirring until all of the metal sodium reacted, it was filtered using a glass filter for 4 to 24 hours, dried in a vacuum state to synthesize sodium betaketonate or sodium betaketoester.

Scheme 2

Preparation of Neutral Ligand Coordinated Metal Reactants

① AgNO ₃ + L → L... AgNO ₃

Where L is phosphite [P (OR2) ₃ , R2 is alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated propyl, fluoro isopropyl, fluoro butyl and fluoro Is one selected from the group consisting of benzene benzyl.

The reaction scheme 2 is described in detail as follows.

In each 100 ml shrink flask, 0.1 mol of anhydrous silver nitrate (AgNO ₃ ) and 0.1 mol of phosphite were added to 20 ml of diethyl ether using a cannula using a double vacuum line. Slowly mix both solutions into the flask. Coordination of silver nitrate and neutral ligand phosphite results in an uncolored liquid.

Scheme 3

Precursor Synthesis According to the Invention

① Na (β-diketonate) + L... AgNO ₃ → L... Ag (β-diketonate) + NaNO ₃

Reaction temperature 0 ℃ / Solvent (ether or tetrahydrofuran)

② Na (β-ketoester) + L... AgNO ₃ → L... Ag (β-ketoester) + NaNO ₃

Reaction temperature 0 ℃ / Solvent (ether or tetrahydrofuran)

Where L is phosphite [P (OR2) ₃ , R2 is alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoro Any one selected from the group consisting of;

The reaction scheme 3 is described in detail as follows.

In a 100 ml Schlenk flask, 0.1 mol of sodium betadiketonate or sodium betaketoester synthesized in [Scheme 1] was dissolved in 20 ml of diethyl ether or tetrahydrofuran, and the solution was slowly removed using a cannula under a double vacuum tube. After mixing to the flask prepared in Scheme 2] the mixture is stirred for 2 hours. The white precipitate was removed using a glass filter, and then the solvent was completely removed in vacuo to synthesize a brown liquid precursor.

Next, the function and action of the precursor according to the present invention will be described.

The silver (Ag) monovalent compound according to the present invention prepared in the manner described above introduces beta diketone and betaketoester ligands to which minimal fluorine groups are introduced, which is not used in the existing silver (Ag) monovalent precursor compounds. By coordinating the phosphite with a new neutral ligand, the silver (Ag) monovalent compound maintains thermal stability and stability in the air, while the volatility and deposition properties of the silver (Ag) precursor are rarely improved in the liquid phase. In particular, compared to the conventional solid-state silver (Ag) monovalent precursor, it can be said to be a breakthrough precursor having a decomposition temperature of about 170 to 200 ℃ while being liquid. This allows for selective deposition even at low temperatures.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to these examples.

Example

Example 1

Preparation of Ag (1,1,1-trifluoro-2,4-pentanedione) trimethyl phosphite

(Herein, 1,1,1-trifluoro-2,4-pentanedione is expressed as tfac and trimethylphosphite is designated as P (OMe) 3)

In the method of Scheme 1, the solvent was stirred for 12 hours using diethyl ether to make H (tfac) to Na (tfac). When the solvent is stirred for 2 hours using tetrahydrofuran in the scheme 2 and scheme 3, a brown liquid (tfac) Ag (P (OMe) ₃ ) is obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.57 CH (s 1H), δ: 3.74 CH ₃ (d 9H), δ: 2.07 CH ₃ (s 3H) / IR (cm ^-1 ) ⇒ υ (C = O ): 1638, υ (C = C): 1495, υ (PO): 778 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 384

Example 2

Preparation of Ag (1,1,1-trifluoro-2,4-pentanedione) triethyl phosphite

(Herein, triethyl phosphite is designated as P (OEt) 3)

In the method of Scheme 1, the solvent was stirred for 12 hours using diethyl ether to make H (tfac) to Na (tfac). When the solvent was stirred for 2 hours using tetrahydrofuran in the scheme 2 and scheme 3, a brown liquid (tfac) Ag (P (OEt) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.56 CH (s 1H), δ: 4.05 CH ₂ (quintet 6H), δ: 2.06 CH ₃ (s 3H), δ: 2.06 CH ₃ (t 9H) / IR ( Cm ⁻¹ ) ⇒ υ (C = O): 1631, υ (C = C): 1501, υ (P-O): 768 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 426

Example 3

Preparation of Ag (1,1,1-trifluoro-2,4-pentanedione) triisopropyl phosphite

(Herein, triisopropylphosphite is designated as P (OiPr) 3)

In the method of Scheme 1, the solvent was stirred for 12 hours using diethyl ether to make H (tfac) to Na (tfac). When the solvent was stirred for 2 hours using tetrahydrofuran in the scheme 2 and scheme 3, a brown liquid (tfac) Ag (P (OiPr) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

1H-NMR (CDCl ₃ ) ⇒ δ: 5.57 CH (s 1H), δ: 4.62 CH (m 3H), δ: 2.06 CH 3 (s 3H), δ: 1.32 CH 3 (d 18 H) / IR (cm-1) ⇒ υ (C = O): 1639, υ (C = C): 1505, υ (PO): 783 / GC-MS (m / z) calcd. for [M +: 107Ag] ⇒ 468

Example 4

Preparation of Ag (1,1,1,5,5,5-hexafluoro-2,4-pentanedione) trimethylphosphite

(Herein, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hereinafter referred to as hfac)

In the method of Scheme 1, the solvent was stirred for 4 hours using pentane to make H (hfac) to Na (hfac). When the solvent was stirred for 2 hours using diethyl ether in the scheme 2 and scheme 3, a brown liquid (hfac) Ag (P (OMe) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.60 CH (s 1H), δ: 3.60 CH ₃ (s 9H) / IR (cm ^-1 ) ⇒ (C = O): 1676, υ (C = C) : 1538,1514, ν (PO): 792 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 438

Example 5

Preparation of Ag (1,1,1,5,5,5-hexafluoro-2,4-pentanedione) triethyl phosphite

In the method of Scheme 1, the solvent was stirred for 4 hours using pentane to make H (hfac) to Na (hfac). When the solvent was stirred for 2 hours using diethyl ether in Scheme 2 and Scheme 3, a brown liquid (hfac) Ag (P (OEt) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.77 CH (s 1H), δ: 4.01 CH ₂ (quintet 6H), δ: 1.29 CH ₃ (t 9H) / IR (cm ^-1 ) ⇒ υ (C = O ): 1681, υ (C = C): 1568,1540, υ (PO): 792 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 480

Example 6

Preparation of Ag (1,1,1,5,5,5-hexafluoro-2,4-pentanedione) triisopropyl phosphite

In the method of Scheme 1, the solvent was stirred for 4 hours using pentane to make H (hfac) to Na (hfac). When the solvent was stirred for 2 hours using diethyl ether in the scheme 2 and scheme 3, a brown liquid (hfac) Ag (P (OiPr) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.89 CH (s 1H), δ: 4.62 CH (m 3H), δ: 1.33 CH ₃ (d 18H) / IR (cm ^-1 ) ⇒ υ (C = O) : 1668, υ (C = C): 1531, υ (PO): 793 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 522

Example 7

Preparation of Ag (ethyl 4,4,4-trifluoro acetoacetate) trimethyl phosphite

(Herein, ethyl 4,4,4-trifluoro acetoacetate, efac hereinafter)

In the method of Scheme 1, the solvent was stirred with silver (Ag) time using pentane to make H (efac) to Na (efac). When the solvent was stirred for 2 hours using diethyl ether in the scheme 2 and scheme 3, a brown liquid (efac) Ag (P (OMe) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 4.97 CH (s 1H), δ: 3.99 CH ₂ (q 2H), δ: 3.65 CH ₃ (b 9H), δ: 1.99 CH ₃ (t 3 H) / IR ( Cm ⁻¹ ) ⇒ υ (C = O): 1671, υ (C = C): 1582, υ (PO): 789 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒414

Example 8

Preparation of Ag (ethyl 4,4,4-trifluoro acetoacetate) triethyl phosphite

In the method of Scheme 1, the solvent was stirred with silver (Ag) time using pentane to make H (efac) to Na (efac). In the scheme 2 and scheme 3, the solvent was stirred for 2 hours using diethyl ether to give a brown liquid (efac) Ag (P (OEt) ₃ ). This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.10 CH (s 1H), δ: 4.05 CH ₂ (quintet 6H), δ: 4.04 CH ₂ (q 2H), δ: 1.32 CH ₃ (t 9H), δ: 1.23 CH ₃ (t 3 H) / IR (cm ⁻¹ ) ⇒ υ (C = O): 1678, υ (C = C): 1579, υ (PO) 798 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 456

Example 9

Preparation of Ag (ethyl 4,4,4-trifluoro acetoacetate) triisopropyl phosphite

In the method of Scheme 1, the solvent was stirred with silver (Ag) time using pentane to make H (efac) to Na (efac). When the solvent was stirred for 2 hours using diethyl ether in Scheme 2 and Scheme 3, brown liquid (efac) Ag (P (OiPr) ₃ ) was obtained. This was analyzed using NMR, IR, GC-MS, and the results are as follows.

¹ H-NMR (CDCl ₃ ) ⇒ δ: 5.12 CH (s 1H), δ: 4.64 CH (s 3H), δ: 4.06 CH ₂ (q 2H), δ: 1.31 CH ₃ (d 18H), δ: 1.23 CH ₃ (t 3 H) / IR (cm −1) ⇒ υ (C = O): 1679, υ (C = C): 1581, ν (PO): 790 / GC-MS (m / z) calcd. for [M ⁺ : ¹⁰⁷ Ag] ⇒ 498

Comparative Example 1

Ag (2,4-pentanedione)

Aldrich reagent was purchased (32349-9).

Comparative Example 2

Ag (1,1,1-trifluoro-2,4-pentanedione)

M.J Shapiro et al. J. Alloys Compd. It was prepared with reference to 1992, 187, 331 paper and K_M.Chi et al. Chem. Vap. Deposition 2001, 7, No. 3, 117 paper data.

Comparative Example 3

Ag (2,4-pentanedione) (COD)

K_M.Chi et al. Chem. Vap. Deposition 2001, 7, No. 3, 117 was prepared with reference to the paper data.

The synthesized precursor, decomposition temperature and properties are summarized in Table 1 below.

Chemical formula condition Decomposition Temperature (℃) Light stability Example 1 (tfac) Ag (P (OMe) ₃ ) Brown liquid 153.7 Good Example 2 (tfac) Ag (P (OEt) ₃ ) Brown liquid 171.4 Good Example 3 (tfac) Ag (P (OiPr) ₃ ) Brown liquid 203.5 Good Example 4 (hfac) Ag (P (OMe) ₃ ) Clear liquid 193.7 Very good Example 5 (hfac) Ag (P (OEt) ₃ ) Clear liquid 217.8 Very good Example 6 (hfac) Ag (P (OiPr) ₃ ) Clear liquid 198.8 Very good Example 7 (efac) Ag (P (OMe) ₃ ) Brown liquid 168.7 Good Example 8 (efac) Ag (P (OEt) ₃ ) Brown liquid 202.7 Good Example 9 (efac) Ag (P (OiPr) ₃ ) Brown liquid 190.1 Good Comparative Example 1 Ag (acac) White solid NA Instability Comparative Example 2 Ag (tfac) White solid 600 Instability Comparative Example 3 Ag (acac) (COD) White solid 200 Instability

NA: Unobservable

acac = 2,4-pentandione

tfac = 1,1,1-trifluoro-2,4-pentanedione

hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione

efac = ethyl 4,4,4-trifluoro acetoacetate

COD = cyclooctadiene

Silver thin film production example

Prior to manufacturing the thin film, the substrates used in the experiments were Si wafer, TiN / SiO ₂ wafer, TiW / SiO ₂ wafer, and each wafer was cut into 1x1㎠ and 1) washed and dried with deionized (DI) water. 2) Soak in Trichloroethane for 20 minutes, 3) Wash with Acetone for 3-5 minutes, 4) Wash with Methanol for 3-5 minutes, 5) Wash with HF (10: 1) for 2-3 minutes, 6) NH4OH for 5 minutes Neutralization, 7) Washed with Deionized (DI) water, followed by a washing process such as drying, and then used for deposition experiments. In addition, after purging with argon gas several times prior to the deposition experiment, the vacuum state was maintained for 2 to 3 hours to keep O ₂ , H ₂ O, etc. from mixing into the thin film, and the precursor was vaporized after heating to a desired deposition temperature. .

Next, the precursor of the present invention using the chemical vapor deposition reaction apparatus of Figure 1 to adjust the substrate to 150-350 ℃, precursor reactor temperature to 80-110 ℃, using a vacuum pump to 0.1 ~ 10㎜Hg pressure of the reactor After the pressure reduction was carried out, a silver (Ag) thin film having a thickness of 200 nm to 5000 nm (measurement device Alpha-step 500 Surface Profiler) was prepared.

Next, silver (Ag) JCPDS No. A single phase with a ratio of (111) / (200) / (220) / (311) of 100-20 / 25/26 of 04-0783 was identified and measured with a resistance tester (4-point probe, CMT-SR 1000N). As a result, it was confirmed that the resistivity of pure silver (Ag) having a specific resistance of 1.5 ~ 1.8μΩ㎝, AES elemental analysis confirmed that the high purity silver (Ag) thin film more than 99%.

As described above, the silver (Ag) precursor of the present invention introduces a beta diketone or beta ketoester ligand and coordinates phosphite with a neutral ligand capable of providing a lone pair of electrons to the central silver (Ag) monovalent. In this way, a liquid organic silver (Ag) monovalent compound having significantly improved volatility and vapor deposition property can be prepared. Through chemical vapor deposition using the same, a high purity, high quality silver (Ag) thin film can be manufactured.

Claims (8)

Silver (Ag) monovalent precursor for producing a silver (Ag) thin film by the chemical vapor deposition method represented by the formula (1). [Formula 1]

Wherein R is hydrogen, an alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Is any one selected from the group consisting of alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, Any one selected from the group consisting of an alkyl group, an alkoxy group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, L is a force Pit groups [P (OR2) 3, R2 in the group consisting of alkyl groups, benzyl, methyl fluoro, ethyl fluoride, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Which one is selected.) The silver (Ag) of claim 1, wherein the alkyl group of R, R1, A, and R2 is any one selected from the group consisting of methyl, ethyl, normal propyl, isopropyl, and butyl. Monovalent precursor. The monovalent silver nitrate coordinated with phosphite [P (OR2) 3, wherein R2 is an alkyl group] and sodium betadiketonate or sodium betaketoester according to claim 1, wherein a neutral ligand capable of providing a lone pair is 2-5. Method for preparing a silver (Ag) monovalent precursor represented by the following formula (1), characterized in that the reaction is prepared by stirring for a metal substitution reaction. [Formula 1]

Wherein R is hydrogen, an alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Is any one selected from the group consisting of alkyl group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, Any one selected from the group consisting of an alkyl group, an alkoxy group, benzyl, methyl fluoro, ethyl fluoro, fluoro normal propyl, isopropyl fluoro, butyl fluoro and benzyl fluoride, L is a force Pit groups [P (OR2) 3, R2 in the group consisting of alkyl groups, benzyl, methyl fluoro, ethyl fluoride, fluorinated normal propyl, isopropyl fluoride, butyl fluoride and benzyl fluoride Which one is selected.) [4] The silver (Ag) of claim 3, wherein the alkyl group of R, R1, A, and R2 is any one selected from the group consisting of methyl, ethyl, normal propyl, isopropyl, and butyl. Monovalent precursor preparation method. The method of claim 3 or 4, wherein the metal substitution reaction is performed at 0 ° C. under an ether or tetrahydrofuran solvent. The monovalent silver nitrate according to claim 3 or 4, wherein a monovalent silver nitrate coordinated with phosphite [P (OR2) 3, R2 is an alkyl group] as a neutral ligand capable of providing a lone pair of electrons is phosphite [P (OR2) 3, R2. A silver (Ag) monovalent precursor production method represented by the formula (1), characterized in that the mixture is prepared by mixing anhydrous silver nitrate to a mixed solution of silver alkyl group] and diethyl ether until it becomes a liquid state of no color. . The method of claim 3 or 4, wherein the sodium beta diketonate is metal sodium in pentane or diethyl ether and cooled to 0 ° C. and then an excess of beta diketonate is added to react all of the metal sodium. Method for producing a silver (Ag) monovalent precursor represented by the formula (1) characterized in that it is prepared by stirring. 5. The method of claim 3 or 4, wherein the sodium betaketoester is added with metallic sodium to pentane or diethyl ether, cooled to 0 ° C, and then an excess of beta-ketoester is added until the metallic sodium is fully reacted. Method for producing a silver (Ag) monovalent precursor represented by the formula (1) characterized in that it is prepared by.

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