JP3232661B2 - Semiconductor storage device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure of a ferroelectric capacitor mainly used for a nonvolatile semiconductor memory device.

[0002]

2. Description of the Related Art Conventionally, for example, Journal of Applied Physics (J. Appl. Phys) 199
As described in 1 year, Vol. 70, No. 1, paragraphs 382 to 388, the crystal of a platinum electrode used in a ferroelectric memory device or the like is made of polycrystal and has a strong crystal orientation ( 1
11) It was oriented.

A conventional example will be described based on a sectional structural view of a ferroelectric element shown in FIG.

That is, a Pb (Zr _x Ti ₁ -x) O ₃ , abbreviated as a PZT film 202, is formed on a lower electrode 201 made of (111) oriented platinum, and an upper electrode 203 is formed thereon. It had been.

The Zr composition ratio X is about 0.5 so that the dielectric constant becomes relatively large.

In addition, the crystallinity of the polycrystal of the PZT film is strongly oriented to (111), affected by the orientation of the underlying platinum.

Writing of information in the ferroelectric memory device is performed according to the direction of polarization of the ferroelectric film in the ferroelectric capacitor.

In the case of the conventional example, the crystal structure of the PZT film has a rhombohedral structure, and polarization is caused because the average positions of the positive ions and the negative ions in the PZT film are shifted in the opposite (111) directions. Is generated.

Here, the positive ions are Pb, Ti,
Zr, and the negative ion is O.

That is, the upper electrode 203 is
When a bias equal to or higher than the coercive electric field of the PZT film 202 is applied so as to have a positive potential with respect to the above, the polarization direction is downward, and when a bias is applied in the opposite direction to the above direction, the polarization direction is upward.

The direction of this polarization corresponds to information 0 and 1.

Therefore, since the polarization inversion of PZT is used as the recording method of the ferroelectric memory device, in order to guarantee 10 years, the switching charge after repeating the polarization inversion 10 ¹⁵ times is guaranteed. Must.

As another conventional example, a journal of applied physics (J. Appl. Phys.
s) 1991, Vol. 69, No. 12, 8352-8
As shown in FIG. 357 and shown in FIG. 3, when forming a (001) -oriented PZT film, the underlayer is made of a MgO (100) single crystal substrate (magnesia) 301 or SrTiO ₃ (10
0) A single crystal substrate (strontium titanate) was used.

That is, the MgO (100) single crystal substrate 3
When Pt is formed by sputtering on Pt. 01, a polycrystalline Pt 302 having a (100) orientation is formed under the influence of the base, and when a PZT film 303 is formed thereon, Pt of the base is formed.
The orientation becomes (001) orientation under the influence of t.

[0015]

However, when a conventional PZT film having a Zr composition ratio of X to 0.5 is formed on a (111) oriented platinum electrode, the PZT film is affected by the underlying platinum electrode (111). Since an oriented PZT film is formed, PZT is oriented while having a strain.

This is because the lattice mismatch caused by a slight difference between the lattice constant of bulk platinum and the lattice constant of bulk PZT is reduced.

Therefore, the structure of the conventional ferroelectric capacitor has a problem that repeated polarization reversal causes film fatigue, resulting in a decrease in remanent polarization and an increase in leak current.

Further, an MgO (100) single crystal substrate, S
A PZT film was formed on an rTiO ₃ (001) single crystal substrate by (00
1) Although it can be oriented and epitaxially grown, it is impossible to form single-crystal MgO or SrTiO ₃ on a substrate on which a field-effect transistor is formed. Therefore, a (001) -oriented PZT film is used. Cannot be integrated with a field-effect transistor.

Therefore, the present invention is to solve such a conventional problem, and an object of the present invention is to provide a semiconductor device having no lattice distortion on the same substrate on which active elements such as field effect transistors are formed. That is, a ferroelectric film having the same crystal structure and lattice constant as the bulk is formed, and
The object of the present invention is to provide a ferroelectric memory device having a warranty period of 10 years or more even if the number of times is ¹⁵ times.

[0020]

According to the present invention, there is provided a semiconductor memory device comprising: (1) an amorphous film formed on a semiconductor substrate on which a moving element is formed, and (100) oriented on the amorphous film. So that
A lower electrode formed, on the lower electrode (001)
A half provided with a dielectric capacitor comprising: an oxide dielectric film having a perovskite crystal structure formed to be oriented; and an upper electrode formed on the oxide dielectric film.
A conductive storage device, wherein the oxide dielectric comprises dititanate.
Lead ruconate Pb (Zr _x Ti _1-x ) O ₃ with Zr composition
Ratio X is 0.1 or more and 0.2 or less or 0.8 or more and 0.9 or less
It is characterized by being below.

Further, according to the semiconductor memory device of the present invention, there is provided: (2) In the above structure, the oxide dielectric of the lower electrode is provided.
The surface in contact with the conductor film must be a (100) oriented platinum layer.
And features.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention will be described with reference to FIGS. 1 (a) to 1 (d).

FIG. 1A shows a part of a normal MOS transistor, which will be briefly described. First, after a thermal nitride film (Si ₃ N ₄ ) is formed on the entire surface of the silicon substrate 101,
A hole is formed in the nitride film at the portion where the LOCOS 102 is to be formed by a photoetching process, and the exposed portion of the silicon substrate is oxidized by wet oxidation using water vapor.
To form

Next, after removing the nitride film used for forming the LOCOS 102, a gate oxide film having a thickness of 150 ° is formed by HCl oxidation.

Polycrystalline silicon 103 is deposited on the entire surface by thermal decomposition of monosilane (SiH ₄ ) gas, and phosphorus (P) is formed by ion implantation at about 10 ²¹ / cm ³ to reduce the resistance value.

Thereafter, the polycrystalline silicon 1 is formed by photoetching and dry etching using CF ₄ gas or the like.
03 is processed as shown in FIG. 1A to form a gate electrode. Next, arsenic (As) is ion-implanted using the polycrystalline silicon as a mask to form a source 104 and a drain 105 by self-alignment.

Further, a film of phosphorus glass 106 is formed by chemical vapor deposition (CVD) containing phosphorus as an interlayer insulating film.

Next, as shown in FIG. 1B, a platinum lower electrode 107 as a lower electrode is formed on the entire surface.

The method for forming the lower electrode 107 will be described in some detail.

As an embodiment, for example, there is a bias sputtering method.

In a direct current (DC) magnetron sputtering method,
While applying a DC bias of minus 500 V to the substrate,
Platinum 107 is formed by sputtering.

Argon (Ar) gas atmosphere, 8 mTorr
30 at a gas pressure of r and an input power density of 5.6 W / cm ² .
By sputtering for 0 seconds, a thickness of 5000 mm, (10
0) An oriented platinum electrode 107 can be formed on the entire surface.

As another embodiment, a normal direct current (DC) magnetron sputtering method without applying a substrate bias by mixing a small amount of oxygen is also possible.

In this case, the partial pressure of argon is 8 mTorr, the partial pressure of oxygen is 0.1 mTorr, and the input power density is 5.6 W / c.
m ^{2, and} the by 250 seconds sputter, 500 thickness
A platinum electrode 107 of 0 ° and (100) orientation can be formed on the entire surface.

Either of the above two methods can be used to form a (100) oriented platinum film on the amorphous phosphorus glass 106.

Further, the above two methods may be combined.

That is, a bias sputtering method in which a slight amount of oxygen is added to a sputtering gas may be used.

Next, as shown in FIG.
No. 07, lead zirconic titanate (PZT) 108 having a thickness of 5000 ° and a (001) -oriented Zr composition ratio X of 0.15.
Is formed by a high frequency (RF) magnetron sputtering method.

The target composition was Pb _1.1 (Zr _0.15 Ti
_0.85 ) O _3.1 .

That is, Zr with respect to the sum of Zr and Ti
Was set to 0.15, and a target composition containing a 10% excess of lead monoxide (PbO) from stoichiometric PZT was used.

The reason why the Zr composition ratio is set to 0.15 is that bulk PZT having this composition ratio has a rectangular parallelepiped crystal structure,
This is because the (001) direction coincides with the direction of polarization. Further, even when the lattice constant of platinum of the lower electrode 107 and the lattice constant of the a-axis of PZT almost coincide with each other and a thin film of PZT is formed, This is because the amount of strain is small and is very effective for film fatigue characteristics such as polarization reversal.

The sputtering conditions were as follows: 9 m of argon gas
Torr, atmosphere of oxygen gas 1 mTorr, substrate temperature 2
00 ° C., RF power density 6 W / cm ² .

After sputtering, PZT having a perovskite structure
In order to obtain, heat treatment was performed at 500 ° C. in an oxygen atmosphere.

By this crystallization heat treatment, a (001) oriented PZT polycrystal could be obtained.

Next, as shown in FIG.
After the upper platinum electrode 109 of 00 ° is formed by DC magnetron sputtering, the lower platinum electrode 107, PZT 108 and upper platinum electrode 109 are processed by ion milling.

Finally, a phosphor glass 110 is formed by plasma-enhanced chemical vapor deposition of tetra-ethyl-ortho-silicate (TEOS), and after a contact hole is opened, an aluminum wiring 111 is formed by DC sputtering, a photo process, and aluminum etching. It is formed by a process.

FIG. 4 is a graph showing a change in switching charge with respect to the number of times of rewriting of the PZT capacitor shown in this embodiment.

Here, the size of the capacitor is set to 100 μm.
× 100 μm and a bias voltage of 5V.

An open circle indicates the case where a capacitor having a (111) -oriented PZT film formed on a conventional (111) Pt lower electrode is used, and a solid circle indicates the embodiment of the present invention (100).
The (001) oriented Pb (Zr
_This is the case where a capacitor having a _0.15 Ti _0.85 ) O ₃ film formed thereon is used.

It can be seen that the ratio of the reduction of the switching charge of the PZT capacitor of the present invention to the number of rewrites, that is, the repetition of the polarization reversal, is much better than the conventional one.

In this embodiment, it is estimated that the magnitude of the switching charge hardly decreases even after rewriting 10 ¹⁵ times.

Further, the leak current after the rewriting was performed 10 ¹² times was conventionally 100 μA / cm ² or more at 5 V,
In the present example, it was as good as 8 μA / cm ² .

In the above embodiment, the composition ratio X of Zr in the PZT film was set to 0.15.
In any of the following, the lattice mismatch with Pt may be very small.

In the above embodiment, PZT has been described, but BaTiO ₃ , PbTiO ₃ , KNbO ₃ , Pb (M
An oxide ferroelectric or oxide paraelectric film having another perovskite crystal structure, such as nNb) O ₃ or (BaSr) TiO ₃ may be used.

In addition, lanthanum (La), neodymium (Nd), bismuth (Bi), niobium (N
b), antimony (Sb), tantalum (Ta) or the like may be used as a dopant.

Further, in the above embodiment, the description has been made using SiO ₂ as the amorphous film formed below the lower electrode.
A silicon nitride film (Si ₃ N ₄ ) may be used.

[0057]

According to the semiconductor memory device of the present invention, an oxide dielectric is integrated on a semiconductor device on which active elements are formed as described above, the crystal of the lower electrode is (100) oriented, and the oxide By making the crystal of the dielectric material film have the (001) orientation, the oxide dielectric can have the bulk crystal structure and lattice constant even as a thin film. Since a dielectric film can be formed, a reduction in switching charge can be prevented even when information is rewritten 10 ¹⁵ times, and a large-capacity semiconductor memory device with excellent reliability can be provided. Has the effect.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a manufacturing process of a semiconductor memory device according to the present invention.

FIG. 2 is a sectional structural view of a ferroelectric element used in a conventional semiconductor memory device.

FIG. 3 is a sectional structural view of a conventional ferroelectric element.

FIG. 4 is a graph showing a change in a switching charge amount with respect to the number of times of rewriting of the semiconductor memory device of the present invention.

[Explanation of symbols]

 Reference Signs List 101 silicon substrate 102 LOCOS 103 polycrystalline silicon 104 source 105 drain 106 phosphorus glass 107 lower platinum electrode 108 PZT 109 upper platinum electrode 110 phosphorus glass 111 aluminum wiring 201 (111) oriented Pt lower electrode 202 PZT film 203 upper electrode 301 MgO single crystal Substrate 302 (100) -oriented Pt 303 PZT film

Claims (2)

(57) [Claims] An amorphous film formed on a semiconductor substrate on which an active element is formed; and an (100) oriented film formed on the amorphous film.
A lower electrode, the upper to the lower electrode (001) is formed to be oriented
A semiconductor storage device having a dielectric capacitor comprising: an oxide dielectric film having a perovskite crystal structure; and an upper electrode formed on the oxide dielectric film.
Thus, the oxide dielectric is made of lead zirconate titanate Pb (Zr _X
Ti _1-X ) O ₃ , and the Zr composition ratio X is 0.1 or more and 0.2 or less or 0.8 or more
A semiconductor memory device characterized by being 0.9 or less. 2. A method according to claim 1, wherein said lower electrode is in contact with said oxide dielectric film.
The surface to be formed is a platinum layer of (100) orientation.
The semiconductor memory device according to claim 1.