# Patent

## Title
Process for fabrication of a ferrocapacitor

## Abstract

In a process for fabricating a ferrocapacitor comprising providing ferroelectric PZT elements over an Al2O3 layer, the Al2O3 layer is covered with a seed layer comprising layers of PZT and TiO2. Then a thicker layer of PZT is formed over the seed layer and crystallized. By this process, the crystallinity of the thick PZT layer is much improved, and its orientation is improved to be in the (111) direction. Furthermore, the seed layer reduces downward diffraction of Pb from the thick PZT layer, such as through the Al2O3 into a TEOS structure beneath.

## Background
TECHNICAL FIELD
The present invention relates to fabrication processes for ferroelectric devices which include one or more ferrocapacitors, and to ferroelectric devices produced by the fabrication processes.
BACKGROUND
Many conventional FeRAM devices include a horizontal ferrocapacitor structure, in which a stack of layers is formed including top and bottom electrodes sandwiching a ferroelectric layer. An alternative “vertical capacitor” structure was suggested in U.S. Pat. No. 6,300,653, the disclosure of which is incorporated herein by reference. A vertical capacitor includes a ferroelectric element sandwiched between electrodes to either side, all at substantially the same level in the FeRAM device.
The vertical capacitors are typically formed over a substructure. The substructure includes various electronic components buried in a matrix (e.g. of TEOS (tetraethylorthosilicate)). The substructure further includes conductive plugs connected to the electronic components, and which extend upwards through the matrix. The upper ends of the plugs typically terminate in TiN/Ir barrier elements, having a top surface flush with the surface of the matrix.
Conventionally, in a process for forming a vertical capacitor, an insulating layer of amorphous Al2O3 is formed over the surface of the matrix, and a thicker layer of ferroelectric material is formed over that, and then crystallized in an oxygen atmosphere. The ferroelectric material may be a perovskite such as PZT (PbZrTiO3). The Al2O3 layer acts as a seed layer for crystallization of the PZT (or other ferroelectric), and has the further function of inhibiting oxygen diffusion into the substructure during the PZT crystallization.
Hardmask elements are then deposited over selected areas of the PZT layer, and the portions of the PZT and Al2O3, which are not protected by the hardmask elements are etched all the way through, forming openings.
The openings are then filled with conductive material such as IrO2, by depositing IrO2 over the entire structure, and chemical-mechanical planarization (CMP) polishing is performed to form a flat upper surface, which is partly the PZT and partly the conductive material. Then, an Al2O3 layer is formed over the surface. The elements of IrO2 constitute electrodes, while the remaining PZT elements constitute the dielectric elements of the ferrocapacitors. At least some of the electrodes may be in electrical contact with the plugs, via the barrier elements.
The vertical capacitor structure has great potential for reducing the cell size, especially if the angle between the horizontal direction and the sides of the remaining PZT elements is high. However, for the PZT to perform effectively it should have a high degree of crystallinity, and furthermore the crystallization should have the correct orientation. Usually, despite the seed layer effect of the Al2O3, PZT deposited on alumina still shows poor crystallinity, with random orientation. This is illustrated in FIG. 1, which shows a diffraction spectrum for various angles for three different types of substrate, corresponding to the lines 1, 2, 3. Line 1 is HT Al2O3 (here “HT” means deposited at a high temperature; line 1 corresponds to 400° C.), line 2 is HT Al2O3 with added oxygen (that is, oxygen is a component of the sputter gas. Thus, whereas line 1 was produced using only Ar as sputter gas, line 2 used an Ar/O2 (ratio 30/20) mixture), line 3 is the case that the Al2O3 substrate is formed by atomic layer deposition (ALD). The peak indicative of the PZT (111) orientation is a position of about 38.5°.
It is known that the crysallinity can be increased by introducing a very thin seed layer (such as TiO2) over the amorphous Al2O3 before the PZT is deposited. FIG. 2 shows the diffraction spectrum for various types of seed. Line 4 shows the case that there is no seed layer (note that line 4 on FIG. 2 is different from line 1 on FIG. 2 due to slightly different deposition conditions), line 5 shows the case that a seed layer is formed of Ti having a thickness of 25 Å, and line 6 shows the case that a seed layer of Ti having a thickness of 25 Å is formed and, before the PZT is deposited, the Ti is oxidized to TiO2. Although the (111) peak at 38.5° is higher in lines 3 and 6 than in lines 1, 2, 4 and 5, it is still relatively low. Also, the PZT morphology is still very poor including voids and nucleation defects. Two electron microscope images, obtained in the experiment illustrated as line 6 of FIG. 2, are shown as FIGS. 3(a) and (b). In FIG. 3(a), the TEOS layer is shown as 7, the Al2O3 as 8 and the PZT as 9. The PZT includes regions indicated by the ovals in FIG. 3(a) with voids and nucleation defects. Furthermore, as shown in FIG. 3(b), the Al2O3 layer 8 and especially the TEOS layer 7 include darker “mushrooms” where lead (Pb) has diffused into the TEOS.
SUMMARY OF THE INVENTION
In certain aspects, the present invention aims to provide a new and useful process for fabricating ferrocapacitors, and to provide devices including such ferrocapacitors.
In general terms, the preferred embodiment of the present invention proposes that in a vertical capacitor fabrication technique in which a relatively thick layer of PZT is formed over an Al2O3 layer, a relatively thin seed layer including both PZT and at least one of TiO2, HfO2 or ZrO2 should be formed over the Al2O3 layer before the PZT is deposited. Most preferably, the oxide is TiO2.
The seed layer preferably includes at least one layer of PZT and also at least one layer of TiO2 (or HfO2 or ZrO2). The layers composing the seed layer may be formed in either order over the substrate in different embodiments of the invention.
The seed layer is typically of a total thickness less than 10 nm.
Typically, the TiO2 (or HfO2 or ZrO2) layer comprised in the seed layer is formed by depositing a layer of Ti (or Hf or Zr), and then oxidizing it, e.g. by RTO (rapid thermal oxidation), simultaneously annealing the PZT and crystallizing the PZT and the TiO2 (or HfO2 or ZrO2) together. All this is preferably before the main PZT layer is deposited.
The ratio of PZT and Ti (or Hf or Zr) in the seed layer may vary, and is preferably selected in accordance with composition of the PZT in the main layer. For example, if the proportions of Pb/Zr in the main PZT are 40:60 by atomic proportions (this can be measured using X-ray fluorescent spectroscope), then we have found the properties of the main layer are optimized if the proportion of PZT/Ti is 3:1 by molecular proportions.
Following the deposition of the main PZT layer, a step is performed to crystallize it.
Specifically, a first expression of the invention is a method of forming a ferroelectric capacitor comprising forming a crystalline PZT layer by a process that includes forming a seed layer over a substructure. The seed layer has at least one PZT layer and a least one metal oxide layer, the metal oxide layer having at least one material selected from the group consisting of TiO2, HfO2 and ZrO2, and combinations thereof. The process performs at least one first annealing step to crystallize the at least one PZT layer and the at least one metal oxide layer together. A layer of amorphous PZT is then deposited over the seed layer and a second annealing step to crystallize the amorphous PZT is performed.



BRIEF DESCRIPTION OF THE DRAWINGS
Preferred features of the invention will now be described, for the sake of illustration only, with reference to the following figures in which:
FIG. 1 shows diffraction spectra for PZT formed over three known Al2O3 structures;
FIG. 2 shows diffraction spectra for PZT formed over an Al2O3 structure, and over two seed layers;
FIG. 3, which is composed of FIGS. 3(a) and 3(b), are electron microscopy images of structures formed in one of the experiments of FIG. 2;
FIG. 4, which is composed of FIGS. 4(a) to 4(d), shows process steps in a method according to the invention;
FIG. 5 is a diffraction spectrum for a result of the method of FIG. 4 and a comparative example; and
FIG. 6 shows an electron microscope image of the structure produced by the method of FIG. 4.



DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention.
Referring to FIG. 4, the steps of a method, which is an embodiment of the invention are shown. In this embodiment Ti is used as an example, although it may be replaced by Hafnium (Hf) or Zirconium (Zr).
The starting point, shown in FIG. 4(a), is a known structure comprising a TEOS layer 11 and an Al2O3 layer 12. In the case that the method of the invention is used to form a ferrocapacitor over a substructure containing electronic components, this TEOS layer 11 may be the top part of that substructure, and may for example include conductive plugs extending upwardly through the layer 11.
In a first step of the method, shown in FIG. 4(b), a Ti layer 13 is formed over the Al2O3 layer 12. This layer is typically of thickness less than about 5 nm.
In a second step of the method, shown in FIG. 4(c), the Ti layer 13 is subjected to an oxidation process, to turn it into TiO2. This may be an RTA process (rapid thermal annealing; this term covers any ambient atmosphere) in an oxygen atmosphere, which amounts to RTO (rapid thermal oxidation) at a temperature of above 500° C. (for example about 650° C.), for a duration of for example 30 seconds.
In a third step of the method, shown in FIG. 4(c), a thin layer of PZT 14 is deposited over the TiO2 layer 13. Then a further layer 15 of Ti is deposited over the PZT layer 14, and the Ti layer 15 is oxidized to form TiO2, e.g., by the RTO process described above. During this process, the layers 14 and 15 crystallize together to form a single seed layer. Note that no RTO step is performed between the deposition of the layer 14 and the deposition of the layer 15.
In a fourth step of the method, shown in FIG. 4(d), a layer PZT 17 is formed over the PZT/Ti seed layer 16. Then, as in conventional techniques, a step of crystallizing the PZT layer 17 is performed.
Referring to FIG. 5, the diffraction spectrum of the PZT layer 17 is shown as line 21. As a comparative example, line 22 of FIG. 5 shows the diffraction spectrum of the case, shown in line 6 of FIG. 2, in which there is a seed layer, which is formed by oxidizing a 25 Å-thick layer of Ti. As will be seen, the PZT peak representing the (111) orientation is much higher in line 21 than in line 22.
FIG. 6 is an electron microscope image of the product of the method of FIG. 4. The PZT shows no obvious nucleation defects, and has a dramatically decreased number of voids, compared to the images of FIG. 3. There is a sharp PZT/Al2O3 interface 23. Furthermore, there is no visible Pb diffusion into the TEOS.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

## Claims

1. A method of forming a ferroelectric capacitor comprising forming a crystalline PZT layer by a process including the steps of:
forming a seed layer over a substructure, the seed layer comprising at least one PZT layer and a least one metal oxide layer, the metal oxide layer comprising at least one material selected from the group consisting of TiO2, HfO2 and ZrO2, and combinations thereof;
performing at least one first annealing step to crystallize the at least one PZT layer and the at least one metal oxide layer together to form a single seed layer;
depositing a layer of amorphous PZT over the seed layer; and
performing a second annealing step to crystallize the amorphous PZT.

2. A method according to claim 1 in which the lowermost layer of the seed layer is PZT.

3. A method according to claim 1 in which the metal oxide is TiO2.

4. A method according to claim 3 in which the lowermost layer of the seed layer is TiO2.

5. A method according to claim 1 in which the total thickness of the seed layer is less than or about equal to 10 nm.

6. A method according to claim 1 in which a further metal oxide layer is formed before the seed layer, the seed layer being formed over the further metal oxide layer.

7. A method according to claim 2 in which the seed layer includes a higher proportion of PZT than of Ti.

8. A method according to claim 7 in which the proportion of PZT/Ti in the seed layer is about 3:1.

9. A method according to claim 6, wherein the further metal oxide layer is TiO2 formed by rapid thermal annealing of Ti.

10. A method of forming a ferroelectric capacitor comprising forming a crystalline PZT layer by a process including the steps of:
forming a seed layer over a substructure, the seed layer comprising at least one PZT layer and a least one metal oxide layer, the metal oxide layer comprising at least one material selected from the group consisting of TiO2, HfO2 and ZrO2, and combinations thereof;
performing at least one first annealing step to crystallize the at least one PZT layer and the at least one metal oxide layer together;
depositing a layer of amorphous PZT over the seed subsequent to said first annealing step layer; and
performing a second annealing step to crystallize the amorphous PZT.

11. A method according to claim 10 in which the lowermost layer of the seed layer is PZT.

12. A method according to claim 10 in which the metal oxide is TiO2.

13. A method according to claim 12 in which the lowermost layer of the seed layer is TiO2.

14. A method according to claim 10 in which the total thickness of the seed layer is less than or about equal to 10 nm.

15. A method according to claim 10 in which a further metal oxide layer is formed before the seed layer, the seed layer being formed over the further metal oxide layer.

16. A method according to claim 11 in which the seed layer includes a higher proportion of PZT than of Ti.

17. A method according to claim 16 in which the proportion of PZT/Ti in the seed layer is about 3:1.

18. The method to claim 15 wherein the further metal oxide layer is TiO2 formed by rapid thermal annealing of Ti.