KR100528961B1 - Method for manufacturing thin copper film using pulsed metal-organic chemical vapor deposition - Google Patents

Abstract

The present invention relates to an organometallic chemical vapor deposition (MOCVD) method, comprising: loading a substrate into a chamber; Injecting a copper monovalent precursor into a source gas into the chamber in a pulsed form to deposit the copper monovalent precursor onto the substrate and injecting a purge gas into the chamber in a pulsed form; The copper monovalent precursor thus relates to a method for forming a copper thin film which is converted to a copper metal by pyrolysis.

Using the method of the present invention, low resistivity, good surface morphology, good step coverage, low impurity, good crystallinity, good A thin film having a smooth surface roughness can be obtained.

Description

Method for manufacturing thin copper film using pulsed metal-organic chemical vapor deposition}

The present invention relates to a method for manufacturing a copper thin film, and more particularly, to a method for manufacturing a copper thin film using an organometallic chemical vapor deposition method.

Although aluminum has been used as a metal wiring material in a metal wiring process of a semiconductor device, it has a weak resistance to signal transfer delay (RC time delay) problems, electromigration and stress migration of aluminum. Many problems, such as hillock caused by stress in the thin film and spiking due to reactivity with silicon, have made copper an alternative.

Since copper has a lower specific resistance than aluminum, it not only improves signal transmission delay but also has higher resistance to electrical and stress transfer than aluminum.

The most studied methods for depositing copper having the above characteristics on substrates are physical vapor deposition (PVD) methods and metal organic sources such as sputtering and evaporation. Chemical vapor deposition (CVD), such as the metal organic chemical vapor deposition method using the said, is mentioned.

First, the sputtering method injects an inert gas such as argon into the vacuum chamber while a high voltage is applied to the target to generate argon ions in the plasma state. At this time, argon ions are sputtered on the surface of the target, and atoms of the target are removed from the surface of the target.

The sputtering method can form a high purity thin film having excellent adhesion with the substrate. However, in the case of depositing a highly integrated thin film having a process difference by the sputtering method, it is very difficult to secure uniformity over the entire thin film. There is a limit to the application.

Next, chemical vapor deposition (CVD) is the most widely used deposition technique. A thin film having a required thickness is deposited on a substrate using a reaction gas and a decomposition gas.

Chemical vapor deposition first injects various gases into the reaction chamber and deposits a thin film of a required thickness on the substrate by chemically reacting gases induced by high energy such as heat, light and plasma.

In addition, the chemical vapor deposition (CVD) increases the deposition rate by controlling the reaction conditions through the ratio and amount of plasma or gases applied by the reaction energy.

However, because of the fast reactions, it is very difficult to control the thermodynamic stability of atoms, and there is a problem of deteriorating the physical and chemical electrical properties of the thin film. In addition, as semiconductor devices become more and more highly integrated, multi-level metallization (MLM) structures have emerged in the metal wiring process, and in addition, the aspect ratio in via / trench structures has increased. It became. Accordingly, the most popular physical vapor deposition (PVD) method is difficult to apply because the void / key hole is generated by the line of sight in the via / trench structure. In the case of organometallic chemical vapor deposition, the limit is increasing as the step ratio increases.

Next came the atomic layer deposition (ALD) method, which sequentially deposits and removes a plurality of atomic layers on a semiconductor substrate, for example, by sequentially injecting and removing reactants into the chamber during semiconductor device fabrication. That's how.

Korean Patent Application No. 10-2001-0038780 discloses an atomic layer deposition method of a metal film and a manufacturing method of a capacitor using the same, but the present method has the advantage of showing excellent film quality and excellent layer covering, but the deposition rate is too slow The disadvantage is that the precursor selection is very difficult.

In conventional organometallic chemical vapor deposition, the copper monovalent precursor is deposited by disproportionation reaction, and the deposition temperature is between 150 ° C and 230 ° C. However, at such a deposition temperature, since the deposition rate is very fast at about 100 nm / min, there is a problem that it is difficult to control a thin film of 100 nm or less. In addition, when deposited at a high speed, as the step ratio increases in the via / trench structure, it is difficult to grow a uniform thin film, and seams may occur.

However, when the conventional organometallic chemical vapor deposition method is carried out at a temperature below 100 ° C., which is a surface reaction rate region, pores are formed in the thin film.

Therefore, there is a demand for a thin film formation method having a good film property while having a deposition rate of about 20 nm / min at low temperature.

The present invention provides a method for forming a copper thin film, which can easily adjust the thickness of the copper thin film, and can form a copper thin film having a uniform and good layer covering effect.

Loading a substrate in the chamber to achieve the technical problem to be achieved by the present invention; Injecting a copper monovalent precursor into a source gas into the chamber in a pulsed form to deposit the copper monovalent precursor onto the substrate and injecting a purge gas into the chamber in a pulsed form; The prepared copper monovalent precursor provides a method for forming a copper thin film which is converted to a copper metal by pyrolysis.

As the copper monovalent precursor, for example, (β-diketonate) CuL _n may be used, wherein L represents a ligand and n = 1 or 2.

L is 3,3-dimethyl-1-butene (3,3-dimethyl-1-butene (DMB), trimethylphosphine (PMe3), 2-butyne (2-butyne), 1,5-cycloocta Diene (1,5-cyclooctadiene: 1,5-COD), vinyltrimethylsilane (VTMS), vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (VTEOS) and allyltrimethylsilane ( It is preferred that it is any one selected from the group consisting of allyltrimethylsilane (ATM).

The β-diketonate is 1,1,1,5,5,5-hexafluoro-2,4-acetylacetonate (1,1,1,5,5,5-hexafluoro-2,4-acetylacetonate : HFAC), more preferably L is DMB.

The purge gas is preferably at least one selected from the group consisting of H ₂ , N ₂ and Ar.

More preferably, the step of injecting the precursor of copper 1 into a pulse form is performed by a bubbler system, and more preferably, the deposition temperature of the copper 1 precursor is about 50 ° C to about 150 ° C.

The injection duration of the copper in the form of a pulse of the precursor is 2.5 to 10 seconds, the injection duration of the injection of the pulse form of the purge gas of step c) is preferably 5 to 20 seconds.

Hereinafter, the present invention will be described in detail.

First, the copper monovalent precursor used as a raw material gas is demonstrated.

Cu (I) precursor is a compound in which one anion ligand is coordinated. Since ionic bonding is weaker than that of Cu (II) precursor, the stability of the precursor itself is inferior but volatility is high.

The type of using Cu (Ⅰ) precursor possible with the present invention can be broadly classified in the form of CuX _n and XCuL. X is a monovalent negatively charged ligand, L is a Lewis base electron pair donor capable of providing a neutral electron pair.

Since CuX did not fill the coordination number of copper ions, the possibility of oligomerization is very high, which may lower the vapor pressure. As the compound of CuX, for example, [Cu (Ot-Bu)] ₄ and [Cu (Ot-Bu) (PPh ₃ )] ₂ can be used.

Compounds of the form XCuL _n (n = 1 or 2) are more preferred because they satisfy all the coordination numbers of the copper ions.

In the copper precursor of the present invention, (β-diketonate) CuL _n (n = 1 or 2) substituted with β-diketonate as a negative ligand may be used as the Cu (I) precursor. β-diketonate ligands help low vapor pressure organometallic compounds to have high volatility, and the neutral ligand, L, serves to stabilize copper ions in low oxidation states as well as to change the deposition temperature range.

As the β-diketonate, CH ₃ of the acetylacetonate group is substituted with CF ₃ having a high electronegativity and a large molecular size, thereby preventing the formation of oligomers and increasing the stretching motion of the carbonyl group to bond metal and oxygen. Since this weakens, 1,1,1,5,5,5-hexafluoro-2,4-acetylacetonate (HFAC), which is a negative ligand capable of increasing vapor pressure, is more preferable.

In addition, even in the (HFAC) CuL _n- based precursor, there are many differences in physical properties and deposition characteristics of various precursors according to the properties of L, which is a neutral ligand coordinated with copper ions. This difference is due to the different binding force between the copper ion and the neutral ligand according to the type of precursor, and this difference also affects the stability of the precursor, the deposition rate of the thin film, and the substrate selectivity. L is, for example, 3,3-dimethyl-1-butene (3,3-dimethyl-1-butene (DMB), trimethylphosphine (PMe3), 2-butyne (2-butyne), 1 1,5-cyclooctadiene (1,5-COD), vinyltrimethylsilane (VTMS), vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (vintetriethoxysilane (VTEOS) And neutral ligands such as allyltrimethylsilane (ATMSS) and the like.

Dual (HFAC) Cu (VTMS) and (HFAC) Cu (DMB) may be preferred precursors because they exist as liquids at room temperature, exhibit some stability, exhibit high deposition rates and good thin film properties.

In the reaction in which the Cu (I) precursor is deposited on the surface, copper is deposited by thermal disproportionation as shown in Scheme 1 below.

The reaction scheme shows that two molecules of Cu (I) compound are transformed into Cu (0) metal and Cu (II) compound which are more stable by intermolecular electron transfer reaction. In this deposition reaction mechanism, it is possible to manufacture pure copper thin films by suppressing impurities contained in thin films that can be generated by organometallic chemical vapor deposition as much as possible.

Typically, the deposition temperature of the metal organic chemical vapor deposition reaction is between about 150 ° C and about 230 ° C. However, in this deposition temperature range, since the deposition rate is very fast at about 100 nm / min, it is difficult to control thin films of 100 nm or less. In addition, as the step ratio increases in the via / trench structure, it is difficult to grow a uniform thin film, and there is a disadvantage that seams may occur.

Thus, in the present invention, the organometallic chemical vapor deposition reaction is preferably carried out at a deposition temperature of not more than 150 ° C, more preferably not more than 100 ° C, which is a surface reaction rate region.

The optimum temperature in the chamber where the deposition reaction occurs depends on the type and nature of the precursor. If the temperature is too low, a thin film may not be formed or a poor film quality may be formed. If the temperature is too high, a thin film may not be formed because the deposition rate is too high. For example, when the copper monovalent precursor is (HFAC) Cu (DMB), the deposition temperature in the chamber is preferably about 50 ° C. to about 150 ° C., more preferably about 60 ° C. to about 120 ° C. Even more preferably about 70 ° C to about 100 ° C.

If the pressure in the chamber in which the deposition reaction occurs is too low, the deposition rate may be excessively lowered. If the pressure is too high, waste of raw materials or contamination by impurities may occur. In view of this, the pressure in the chamber in which the deposition reaction takes place may be about 1 to about 10 torr.

The injection method of the source gas and the purge gas is a pulse type injection method. The pulsed injection method is to maintain the amount of gas injected over time as if it were a pulse, and refers to a method of injecting in such a way that the period of injecting and the period of not injecting are repeated. In the method of injecting the source gas and the purge gas, as soon as the injection of the precursor of copper 1 is stopped in the form of pulse, the injection of purge gas is performed in the form of pulse, and as soon as the injection of the purge gas into the form of pulse is stopped. It is characterized by repeating the method of injecting the precursor in the form of a pulse two or more times.

As a device for injecting the raw material gas, various known devices may be used, and for example, a bubbler system may be used. The bubbler system is a device for supplying vapor of the precursor to the chamber while the carrier gas passes through the precursor in the liquid phase. In the bubbler system, the injection amount of the precursor can be easily controlled by changing the temperature to adjust the vapor pressure of the precursor and the flow rate of the carrier gas.

As the purge gas, an inert gas or a gas with low activity may be used without particular limitation, and specific examples, for example, argon or nitrogen may be used, and in particular, a reducing gas such as hydrogen may be used for the reduction of the precursor.

While maintaining the chamber at a pressure of 1 to 10 torr, raw gas is injected into the reactor in which the substrate is located for 2.5 to 10 seconds per cycle and purge gas is injected for 5 to 20 seconds per cycle.

If the duration of the injection cycle of the reaction gas is too long, the effect of the pulse injection type MOCVD may not be properly expressed, and if it is too short, the deposition rate may be reduced. In view of this, the duration of the injection cycle of the reaction gas may be about 2.5 seconds to about 10 seconds.

If the duration of the injection cycle of purge gas is too long, the process time may be excessively long, and if it is too short, the purge effect may not be sufficient. In view of this, the duration of the injection cycle of purge gas may be about 5 seconds to about 20 seconds.

After the injection of the raw material gas, the injection of the purge gas is started immediately, and the injection of the raw material gas is repeated again after the injection of the purge gas is repeated, and the copper precursor is deposited on the substrate two or more times.

At this time, it is necessary to adjust the vapor pressure of the raw material gas is sufficient, which can change the vapor pressure of the raw material by adjusting the temperature of the container containing the raw material. In addition, the flow volume of raw material gas can be adjusted with a flow regulator.

As the substrate on which the copper thin film of the present invention is deposited, a conventional substrate used in the art may be used, and for example, a substrate on which Ta is deposited on Si may be used.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example

As the substrate, a Si substrate on which Ta was deposited was used. Ta is known as a diffusion barrier film, and adhesion with copper is known to be good, and a substrate on which Ta is deposited was used.

(HFAC) Cu (DMB) was used as the copper monovalent precursor, and the purge gas was subjected to a deposition reaction using argon gas. Under the reactor pressure of 1 torr, the copper thin film was prepared by injecting the raw gas into the reactor for 5 seconds per cycle and purging gas for 20 seconds per cycle at a flow rate of 200 sccm. At this time, the temperature of the vessel containing (HFAC) Cu (DMB) was room temperature, Ar was used at a flow rate of 40 sccm as a carrier gas for bubbling. The temperature of the line to the reactor was maintained at 45 ° C and the temperature of the substrate at 70 ° C.

Comparative example

A copper thin film was prepared in the same manner as in Example, except that a conventional organometallic chemical vapor deposition method in which a raw material gas and a purge gas were not injected in a pulse form was used.

As a substrate, a substrate on which Ta was deposited on Si was used, and (HFAC) Cu (DMB) was used as a copper monovalent precursor, and a purge gas was deposited using argon gas. The temperature of the vessel containing (HFAC) Cu (DMB) was maintained at room temperature, the temperature of the line to the reactor was 45 ° C, and the temperature of the substrate was 70 ° C.

Deposition Rate

In the case of the copper thin film deposited by the pulse injection-type organometallic chemical vapor deposition method, the deposition rate was about 0.75 증착 / cycle as shown in Figure 1a. In the case of the copper thin film deposited using the organometallic chemical vapor deposition method, the deposition rate was about 17.23 Å / min as shown in Figure 1b.

Based on the raw material gas injection amount (or injection time), the deposition rate of the copper thin film deposited by the organometallic chemical vapor deposition method is about 2 times higher than the deposition rate of the copper thin film deposited by the pulse injection type organometallic chemical vapor deposition method. It can be seen that. And, it can be seen that the deposition rate of the copper thin film deposited by the pulse injection type organic metal chemical vapor deposition method is faster than the deposition rate of the copper thin film deposited by the conventionally known atomic layer deposition method.

Measurement of resistivity change of deposited copper thin film

The resistivity of the copper thin film deposited by the pulse injection type organometallic chemical vapor deposition method and the organometallic chemical vapor deposition method was compared. In general, the thicker the resistivity of a copper thin film, the smaller the thickness is affected by the substrate. The specific resistance of the copper thin film formed by the pulse injection-type organometallic chemical vapor deposition method of the present invention was 6 to 129 μm cm depending on the thickness thereof, and the specific resistance of the copper thin film formed by the conventional organic metal chemical vapor deposition method was 105 to 322 μm cm. A comparative graph of the specific resistance according to both methods is shown in FIG. 2.

In the case of the pulse-injected organometallic chemical vapor deposition method, the specific resistance value is different according to the change of the argon purge pulse time, but the specific resistance drops as the argon purge pulse time increases. When the argon purge pulse time was 5 s or more, it tended to be almost saturated.

In addition, although the copper thin film deposited by the pulse injection type organometallic chemical vapor deposition method has a lower resistivity value than the copper thin film deposited by the organometallic chemical vapor deposition method, the copper thin film was generally higher than the bulk copper (1.67 μΩ-cm). This is because the deposited thin film is a thin film of less than 100nm, due to the effect of electron scattering caused by low grain size due to low deposition temperature.

Surface shape of the deposited copper thin film

The morphologies of the copper thin films deposited by the pulse injection type organometallic chemical vapor deposition method and the organometallic chemical vapor deposition method were compared. As shown in FIG. 3A, in the case of the copper thin film deposited by the pulse injection-type organometallic chemical vapor deposition method, a uniform and dense thin film was shown. Meanwhile, as shown in FIG. 3B, a void was generated in the case of the copper thin film deposited by the organic metal chemical vapor deposition method. These voids tended to decrease or shrink as the thickness increased, but did not disappear. Such void formation is also one of the causes of increasing the specific resistance of the thin film, and the reason why the specific resistance of the copper thin film deposited by the organic metal chemical vapor deposition method is high can be found here as well as the impurities.

Crystallinity and Orientation of Deposited Copper Thin Films

The crystallinity and orientation of the copper thin films deposited by the pulse injection type organometallic chemical vapor deposition method and the organometallic chemical vapor deposition method were investigated. As a result, as shown in FIG. 4A, the copper thin film deposited by the pulse injection type metal organic chemical vapor deposition showed sharp peaks at Cu (111) and Cu (200) at 2θ values of 43.4 ° and 50.6 °. On the other hand, as shown in FIG. 4B, the copper thin film deposited by the organometallic chemical vapor deposition method showed a weak 2θ value at 43.4 ° and was hardly observed at 50.6 °. These results show that the copper thin film deposited by the pulse injection organometallic chemical vapor deposition method is much more crystalline than the copper thin film deposited by the organometallic chemical vapor deposition method.

Impurity Content in Deposited Copper Thin Films

The amount of impurities in the copper thin film deposited by the pulse injection type organometallic chemical vapor deposition method and the organometallic chemical vapor deposition method were compared. In both cases, oxygen was the main impurity in the thin film, and the content was about 3% by the pulse injection-type organometallic chemical vapor deposition method, as shown in FIG. 5A. On the other hand, as shown in Figure 5b by the organic metal chemical vapor deposition method was about 14%. The amount of such impurities is a factor influencing the specific resistance, and one of the reasons why the specific resistance of the copper thin film deposited by the organometallic chemical vapor deposition method is high is considered to be such impurity content.

Layer Covering Effect of Deposited Copper Thin Films

The layer covering of copper thin films was investigated using pulse-injected organometallic chemical vapor deposition (CVD). 6 is a cross-sectional SEM photograph of a copper thin film obtained by performing pulse injection type organometallic chemical vapor deposition of about 650 cycles using a substrate having a step ratio value of 10. The results confirmed a film with very good layer covering. The ratio of the thickness of the thin film deposited on the surface and the thickness deposited on the bottom of the trench structure was almost 1.

According to the method of the present invention, a copper thin film grown by pulse injection type organometallic chemical vapor deposition at a low temperature of about 70 to about 100 ° C. or less has remarkable in terms of resistivity, surface morphology, cross section, impurity content, crystallinity, directionality, and layer covering. It shows an improved effect and can be applied to next generation semiconductor devices.

Figure 1a is a graph showing the deposition rate of the copper thin film deposited by the pulse injection type organic metal chemical vapor deposition method according to an embodiment of the present invention.

1B is a graph showing the deposition rate of a copper thin film deposited by a simple organometallic chemical vapor deposition method according to a comparative example.

2 is a graph showing the resistivity of a copper thin film deposited by a pulse injection type organometallic chemical vapor deposition method according to an embodiment of the present invention and a simple organometallic chemical vapor deposition method according to a comparative example.

3A is a view showing the surface shape of a copper thin film deposited by a pulse injection type organometallic chemical vapor deposition method according to an embodiment of the present invention.

3B is a view showing the surface shape of a copper thin film deposited by a simple organometallic chemical vapor deposition method according to a comparative example.

4A is a graph illustrating crystallinity and orientation of a copper thin film deposited by a pulse injection type organometallic chemical vapor deposition method according to an exemplary embodiment of the present invention.

4B is a graph showing the crystallinity and the orientation of the copper thin film deposited by the simple organic metal chemical vapor deposition according to the comparative example.

5A is a graph showing the amount of impurities in a copper thin film deposited by a pulse injection type organometallic chemical vapor deposition method according to an embodiment of the present invention.

5B is a graph showing the amount of impurities in the copper thin film deposited by the simple organic metal chemical vapor deposition according to the comparative example.

6 is a view showing a layer covering of a copper thin film deposited by a pulse injection type organic metal chemical vapor deposition according to an embodiment of the present invention.

Claims (10)

Loading a substrate into the chamber; Injecting a copper monovalent precursor into a pulse form into the chamber as a source gas, chemically depositing the copper monovalent precursor onto the substrate, and injecting a purge gas into the chamber in a pulse form, The copper monovalent precursor deposited on the substrate is converted to a copper metal by pyrolysis. 2. The method of claim 1, wherein the copper monovalent precursor is (β-diketonate) CuL _n , L represents a ligand, and n is 1 or 2. 3. The method of claim 2, wherein L is 3,3-dimethyl-1-butene (3,3-dimethyl-1-butene (DMB), trimethylphosphine (PMe3), 2-butyne (2-butyne), 1,5-cyclooctadiene (1,5-cyclooctadiene: 1,5-COD), vinyltrimethylsilane (VTMS), vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (vinyltriethoxysilane: VTEOS And allyltrimethylsilane (ATMS). The method of claim 2, wherein the β-diketonate is 1,1,1,5,5,5-hexafluoro-2,4-acetylacetonate (1,1,1,5,5,5-hexafluoro -2,4-acetylacetonate: HFAC) copper thin film formation method characterized in that. 3. The method of claim 2, wherein the β-diketonate is HFAC, and L is DMB. The method of claim 1, wherein the purge gas is at least one selected from the group consisting of H ₂ , N ₂ , and Ar. The method of claim 1, wherein the injecting the copper precursor in the form of a pulse is performed by a bubbler system. The method of claim 1, wherein the deposition temperature of the copper 1 precursor is 50 to 150 ℃. The method of claim 1, wherein the deposition temperature of the copper 1 precursor is 70 to 100 ℃. The method of claim 1, wherein the injection duration of the copper in the form of a pulse of the precursor is 2.5 to 10 seconds, the injection duration of the injection of the pulse form of the purge gas of step c) is 5 to 20 It is a candle, The formation method of the copper thin film characterized by the above-mentioned.