# Patent

## Title
PCMO thin film with resistance random access memory (RRAM) characteristics

## Abstract

PrCaMnO (PCMO) thin films with predetermined memory-resistance characteristics and associated formation processes have been provided. In one aspect the method comprises: forming a Pr3+1−xCa2+xMnO thin film composition, where 0.1<x<0.6; in response to the selection of x, varying the ratio of Mn and O ions as follows: O2−(3±20%); Mn3+((1−x)±20%); and, Mn4+(x±20%). When the PCMO thin film has a Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96 composition, the ratio of Mn and O ions varies as follows: O2−(2.96); Mn3+((1−x)+8%); and, Mn4+(x−8%). In another aspect, the method creates a density in the PCMO film, responsive to the crystallographic orientation. For example, if the PCMO film has a (110) orientation, a density is created in the range of 5 to 6.76 Mn atoms per 100 Å2 in a plane perpendicular to the (110) orientation.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention generally relates to integrated circuit (IC) memory fabrication and, more particularly, to a PrxCa1−xMnO3 (PCMO) memory film and associated film process.
2. Description of the Related Art
In order to meet the requirements of low power, low operation voltage, high-speed, and high-density memory applications, electrically alterable resistors are being investigated that can be fabricated from PCMO. Metalorganic chemical vapor deposition (MOCVD), sputtering, laser ablation, and metalorganic deposition (MOD) methods can be used, along with appropriate surface treatments, to deposit PCMO on various substrates. The different deposition methods are being investigated to address the control of specific interfacial properties of the PCMO, such as lattice mismatch, trapped charge density, as well as bulk properties such as grain size and film. Reversible and non-volatile resistance changes in the PCMO film are desirable using either bipolar or unipolar pulsed biasing. Therefore, an understanding the relationship between memory characteristics and PCMO thin film material structure is sought. PCMO also exhibits colossal magnetoresistive (CMR) properties. These are also strongly affected by thin film crystal structure. An understanding of the relationship between crystal structure and an electrically alterable resistance suitable for RRAM devices is desired.
It would be advantageous if the memory resistance characteristics of a PCMO film could be controlled and optimized by the judicious choice of crystallization and orientation of PCMO thin films.
SUMMARY OF THE INVENTION
The present invention describes processes for forming PCMO resistance-memory characteristics that are responsive to controllable deposition attributes such as film composition, structure, and crystallographic orientation.
Accordingly, a method is provided for forming a PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics. In one aspect the method comprises: forming a Pr3+1−xCa2+xMnO thin film composition, where 0.1<x<0.6; in response to the selection of x, varying the ratio of Mn and O ions as follows:

    
    
        O2−(3±20%);
        Mn3+((1−x)±20%); and,
        Mn4+(x±20%).
    
    


For example, when the PCMO thin film has a Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96 composition, the ratio of Mn and O ions varies as follows:

    
    
        O2−(2.96);
        Mn3+((1−x)+8%); and,
        Mn4+(x−8%).
    
    


In another aspect, the method comprises forming a PCMO thin film with a crystallographic orientation; and, creating a density in the PCMO film, responsive to the orientation. For example, if the PCMO film has a (110) orientation, a density is created in the range of 5 to 6.76 Mn atoms per 100 Å2 in a plane perpendicular to the (110) orientation.
In another aspect, the method comprises: forming a bottom electrode; forming a PCMO thin film with a crystallographic orientation overlying the bottom electrode; and, creating a lattice mismatch in the PCMO film, responsive to the orientation, between the PCMO thin film and the bottom electrode. For example, if the PCMO film has a (110) orientation, then a lattice mismatch of less than 30% is created between the PCMO thin film and the bottom electrode.
In a different aspect, the method comprises: forming a PCMO thin film with a crystallographic orientation; and, creating a PCMO film with a selectable resistance state, responsive to the orientation. For example, if the PCMO film has a (001) orientation, then the PCMO film resistance state can be written to a high resistance in the range of 10 to 1000 kilo ohms, using ±(2 to 10) volt (V) pulse, with a duration in the range of 5 nanosecond (ns) to 50 microseconds. Further, the (001) PCMO can be reset to a low resistance in the range of 500 ohms to 10 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds.
In another aspect, the method comprises: forming a PCMO thin film with a crystal grain size; and, creating a PCMO film with a selectable resistance state, responsive to the grain size. For example, if the PCMO film is formed with an average crystal grain size in the range of 3 to 40 nanometers (nm), then the PCMO film can be written to a high resistance of greater than 225 kilo ohms, using 5 V pulse of less than 100 ns, or reset to a low resistance of less than 10 kilo ohms, using a 3 V pulse of less than 10 microseconds.
In one aspect, the method comprises creating a super lattice structure with an ordered distribution in the PCMO film, responsive to the PCMO film composition. For example, if the PCMO thin film has a Pr3+0.50Ca2+0.50MnO0.3 composition, then a distribution is created as follows:

    
    
        Z(Mn3+)PrMnO3: Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
    
    


Additional details of the above-described methods, and a PCMO device with memory characteristics responsive to film attributes such as composition, structure, and crystallographic orientation, are presented below.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a drawing illustrating perovskite cubic structures.
FIG. 2 is a drawing illustrating the PrMnO3 lattice structure.
FIG. 3 is a drawing depicting the Gibbs free energies for the formation of Pr and Mn oxides.
FIGS. 4A and 4B are drawings illustrating the mechanism of reversible resistive switching properties in a CaMnO3 unit.
FIG. 5 is a drawing depicting the relationship between composition and lattice structures of Pr1−xCaxMnO3.
FIG. 6 is a drawing depicting the band gap as a function of x value and oxygen vacancies.
FIG. 7 is a diagram depicting the distribution of PrMnO3 and CaMnO3 subunits, as a function of x, in Pr1−xCaxMnO3 materials.
FIGS. 8A and 8B are drawings showing the direction from Mn3+ ions in PrMnO3, to oxygen vacancies, oriented toward a top electrode.
FIGS. 9A and 9B are drawings depicting the direction of electron flow when opposite polarity pulses are applied to the top electrode.
FIGS. 10A and 10B are drawings showing the directionality of electron jumps between Mn3+ and Mn4+ ions.
FIGS. 11A and 11B show electron flow when the PrMnO3 and CaMnO3 subunit layers are reversed with respect to the bottom electrode.
FIGS. 12A, 12B, 12C depict the (110), (011), and (101) orientations, respectively, of PCMO thin films.
FIG. 13 shows an x-ray pattern of PCMO with partial (110) orientation.
FIGS. 14A and 14B depict the (100) and (010) orientations of PCMO thin films, respectively.
FIG. 15 shows the (001) orientation (marked ABCD) of PCMO thin films.
FIG. 16 shows the x-ray pattern of PCMO thin films with (001) orientation.
FIG. 17 depicts the EDX pattern of the PCMO thin film of FIG. 16.
FIG. 18 depicts the switching properties of c-axis oriented PCMO thin films.
FIG. 19 shows the x-ray pattern of a PCMO thin film with nanosized polycrystalline materials.
FIG. 20 depicts the unipolar switching properties of the PCMO thin film of FIG. 19.
FIG. 21 is a partial cross-sectional view of the present invention Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% O2−3±20% (PCMO) thin film memory-resistance device.
FIGS. 22 through 27 are flowcharts illustrating different aspects of the present invention method for forming a PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Some general relationships between PCMO physical attributes, responsive to deposition procedures, and resistance-memory characteristics will be initially presented. Detailed analysis of these general relationships is presented below in the Functional Description Section of the application.
The first aspect of the present invention should be considered with respect to FIGS. 4A, 4B, and Table 1, below. A PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics comprises a Pr3+1−xCa2+xMnO composition, where 0.1<x<0.6; and, a ratio of Mn and O ions is responsive to the composition as follows:

    
    
        O2−(3±20%);
        Mn3+((1−x)±20%); and,
        Mn4+(x±20%).
    
    


When the composition is Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96, then the ratio of Mn and O ions is as follows:

    
    
        O2−(2.96);
        Mn3+((1−x)+8%); and,
        Mn4+(x−8%).
    
    


Further, the PCMO film has a 13.3% oxygen vacancy.
In a second aspect of the invention, considered with respect to Table 1 and FIGS. 12A–12C, a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film comprises a crystallographic orientation, and a density responsive to the orientation. When the crystallographic orientation is a (110) orientation, the density is in the range of 5 to 6.76 Mn atoms per 100 Å2 in a plane perpendicular to the (110) orientation (the <110>). Further, a distance of 3.855 Å exists between closest (the two closest) Mn atoms, responsive to the (110) orientation.
When the crystallographic orientation is in a (001) orientation, the density is in the range of 5 to 6.73 Mn atoms per 100 Å2 in a plane perpendicular to the (001) orientation, and a distance of 3.840 Å exists between the two closest Mn atoms, responsive to the (001) orientation.
FIG. 21 is a partial cross-sectional view of the present invention Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film memory-resistance device. The device 100 comprises a bottom electrode (BE) 102, a PCMO thin film 104 overlying the bottom electrode 102, and a top electrode (TE) 106. The bottom electrode 102 can be a material such as Pt, Ir, Al, or TiN. In some aspects, a buffer layer 108 is interposed between the PCMO thin film 104 and the bottom electrode 102 formed from a material such as InO2 or ZnO.
The PCMO thin film 104 has a crystallographic orientation, and a lattice mismatch between the PCMO thin film 104 and the bottom electrode 102 (or buffer layer 108), responsive to the crystallographic orientation. When the PCMO thin film 104 has a (110) orientation, then the lattice mismatch of less than 30%. Likewise, when the PCMO thin film 104 has a (001) orientation, the lattice mismatch is less than 30%.
In a different aspect (see FIGS. 18 and 20), the Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film has a crystallographic orientation and a selectable resistance state, responsive to the crystallographic orientation. When the crystallographic orientation is in a (001) orientation, the selectable resistance state is a high resistance in the range of 10 to 1000 kilo ohms, using ±(2 to 10) volt (V) pulse, with a duration in the range of 5 nanosecond (ns) to 50 microseconds, or a low resistance in the range of 500 ohms to 10 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds.
If the PCMO crystallographic orientation is in a (110) orientation, the selectable resistance state is a high resistance in the range of 10 to 1000 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds, or a low resistance in the range of 500 ohms to 10 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds.
In another aspect, see FIGS. 19 and 20, the Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film comprises a crystal grain size, and a selectable resistance state, responsive to the grain size. If the crystal grain size is in the range of 3 to 40 nanometers (nm), then the selectable resistance state is a high resistance of greater than 225 kilo ohms, using 5 V pulse of less than 100 ns, or a low resistance of less than 10 kilo ohms, using a 3 V pulse of less than 10 microseconds.
If the crystal grain size in the range of 40 nm to epitaxial, then the selectable resistance state can be a high resistance of greater than 300 kilo ohms, using −5 V pulse of less than 50 microseconds, or a low resistance of less than 10 kilo ohms, using a +5 V pulse of less than 50 microseconds.
In another aspect, see FIG. 7, a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film comprises a composition, and a super lattice structure of with an ordered distribution, responsive to the composition. For example, if the composition is Pr3+0.50Ca2+0.50MnO0.3, then the super lattice structure ordered distribution is:
Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
If the composition is Pr3+0.67Ca2+0.33MnO0.3, then the super lattice structure ordered distribution is:
2Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
If the composition is Pr3+0.75Ca2+0.25MnO0.3, then the super lattice structure of ordered distribution is:
3Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
Functional Description
FIG. 1 is a drawing illustrating perovskite cubic structures. Pr1−xCaxMnO3 is an electrically alterable resistive material whose memory resistance characteristics are related to the PCMO lattice structure. The unit cell of Pr1−xCaxMnO3 consist of two subunits units: PrMnO3 and CaMnO3. The ideal lattice of each unit has the same perovskite cubic structure, as shown in the figure.
In the case of the Pr1−xCaxMnO3 series, the end members PrMnO3 and CaMnO3 have an orthorhombic structure belonging to the same space group Pbnm, but the distortion of the latter is almost negligible so that its structure may be regarded as quasicubic. The change of the lattice parameters when passing from x=0 to x=1 is, however, not monotonic and exhibits some anomalies. Similar peculiarities, though different in detail, seem to exist in other rare earth manganese perovskites. Further, both PrMnO3 and CaMnO3 are antiferromagnetically ordered and insulating at low temperatures (types Ay and G, respectively). But in the range of 0<x<0.4 a spontaneous ferromagnetic moment appears that has been ascribed to the strong double exchange interactions Mn3+—O2—Mn4+, which results in a material transformation from (Mott) insulator to metallic conductor.
FIG. 2 is a drawing illustrating the PrMnO3 lattice structure. PrMnO3 units have Pr3+ and Mn3+ ions. The deviations of Mn—O1—Mn and Mn—OII—Mn angles from 180° (which is the angle in ideal cubic perovskites) manifest the buckling and are the cause of the lattice distortion (especially the elongation of the b axis) in orthorhombic perovskites. The increase of the b parameter is markedly enhanced in PrMnO3 and other samples with high Mn3+content due to the eg orbital ordering shown in FIG. 2.
FIG. 3 is a drawing depicting the Gibbs free energies for the formation of Pr and Mn oxides. According to simple calculations of the Gibbs free energy of oxides, both Mn3+ and Mn4+ and Pr3+ and Pr4+are stable at room temperature, as shown. In PrMnO3 units, the Pr3+ and Mn3+ ions are stable. PrMnO3 are antiferromagnetically ordered and insulating at low temperatures. Under certain conditions, such as those existing with CaMnO3, or with oxygen vacancies in PrMnO3 units, the bond gap of the PrMnO3 material decreases. Then, the Mn3+ ion can lose a free electron and change to Mn4+as shown in equation 1.

Mn3+→Mn4++e−  (1)

Because the Mn3+in PrMnO3, and Mn4+in CaMnO3 subunits have almost the same octahedral cage formed by oxygen ions enclosing Mn ions, double exchange interactions Mn3+—O2—Mn4+may occur. Oxygen vacancies further enhance the double exchange interactions Mn3+—O2—Mn4+. Therefore, doping Ca into PrMnO3 to form PCMO, in particular Pr1−xCaxMnO3 (0<x<0.4), results in an electrically conductive material. Moreover, the CaMnO3 subunit formed in the cubic perovskite ABX3 structure has a lattice constant of 3.73 Å. Mn ions are sixfold coordinated with oxygen ions along the Cartesian axis, while Ca ions are twelvefold coordinated with oxygen ions lying along its (110) directions. Six oxygen ions form an octahedral cage for the Mn ions, and the cage is linked by oxygen ions. Naturally, the CaMnO3 subunits have Ca2+ and Mn4+ ions. Because of the strong electronegativity of oxygen, essentially no electrons are available to transform an Mn4+ ion into an Mn3+within these subunits. CaMnO3 has a large band gap and bulk CaMnO3 is found to be an insulator. On the other hand, due to formation of defects such as oxygen vacancies, the band gap of CaMnO3 may be reduced, in which case the Mn4+ ion may accept an electron to form Mn3+in these subunits as shown in equation 2.

Mn4++e−→Mn3+  (2)

In this way, Mn3+ ions may form within CaMnO3 subunits with oxygen vacancies, as shown in equation 3.

CaMnO3→2[Mn3+]′[Mn4+]+Oo+V.o  (3)

FIGS. 4A and 4B are drawings illustrating the mechanism of reversible resistive switching properties in a CaMnO3 unit. If the valence electrons of the Mn3+ ions in Mn4+positions get energy, by any means such as thermal or electrical energy, the electrons can jump to oxygen vacancies or jump back to the Mn3+ ions in Mn4+positions. On the other hand, when PrMnO3 units exist in CaMnO3 material, the valence electrons of the Mn3+ ions in PrMnO3 units that get energy (thermal, electrical energy, etc.), can jump to Mn4+ ions in CaMnO3 units, or jump back to the Mn3+ ions in CaMnO3 units, which is the double exchange interaction Mn3+—O2—Mn4+. Oxygen vacancies provide the space for the double exchange interactions Mn3+—O2—Mn4+. In this way, Pr1−xCaxMnO3 materials can have both lower resistance and higher resistance states. In the state where electrons jump into oxygen vacancies or the Mn4+position in CaMnO4 units (FIG. 4A), a lower resistance results. In the state where electrons jump back to Mn3+ ions, a higher resistance results, as shown in FIG. 4B.
For Pr1−xCaxMnO3 (0<x<1) materials, the lattice constants, orthorhombic distortion D, and the valence distribution are shown in Table 1, cross-referenced to an increasing value of x (increasing CaMnO3 subunits to PCMO). From Table 1, it follows that when x=0.3 or 0.6, PCMO materials have a maximum concentration of Mn3+ ions (8%) in CaMnO3 subunits and oxygen vacancies (4%).
The room temperature lattice constants, orthorhombic distortion D, and the valance distribution in the Pr1−xCaxMnO3 materials












TABLE 1





x
a Å)
b Å)
c Å)
D (%)
Valence distribution





















0




Pr3+0.994Mn3+0.958Mn4+0.036O2−3
(4)


0.1
5.442
5.617
7.635
1.59
Pr3+0.89Ca2+0.11Mn3+0.91Mn4+0.09O2−2.985
(3)


0.2
5.442
5.552
7.657
1.01
Pr3+0.80Ca2+0.2Mn3+0.81Mn4+0.19O2−2.995
(3)


0.3
5.426
5.478
7.679
0.41
Pr3+0.70Ca2+Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96
(3)


0.4
5.415
5.438
7.664
0.17
Pr3+0.60Ca2+0.40Mn3+0.64Mn4+0.36O2−2.98
(3)


0.5
5.395
5.403
7.612
0.14
Pr3+0.50Ca2+0.50Mn3+0.55Mn4+0.45O2−2.975
(3)


0.6
5.375
5.375
7.60
—
Pr3+0.40Ca2+0.60Mn3+0.48Mn4+0.52O2−2.96
(3)


0.7
5.349
5.349
7.543
—
Pr3+0.30Ca2+0.70Mn3+0.33Mn4+0.67O2−2.985
(3)


0.8
5.318
5.318
7.521
—
Pr3+0.20Ca2+0.80Mn3+0.25Mn4+0.75O2−2.97
(3)


0.9
5.300
5.300
7.495
—
Pr3+0.10Ca2+0.90Mn3+0.23Mn4+0.77O2−2.93
(3)


1




Ca2+Mn3+0.16Mn4+0.84O2−2.92
(4)









FIG. 5 is a drawing depicting the relationship between composition and lattice structures of Pr1−xCaxMnO3. Due to the absence of double exchange interactions: Mn3+—O2—Mn4+, for x=0.6, a composition of Pr1−xCaxMnO3 with x=0.3 may be the best candidate material for an RRAM device in some applications. From the figure, in the composition range 0<x<0.4, Pr1−xCaxMnO3 materials exhibit a larger lattice distortion. In contrast, for x>0.4, a smaller lattice distortion can be found.
Next, the mechanism of reversible resistive switching properties in a PCMO material is described. Based on above analysis, the electrically alterable resistive properties of PCMO materials may come from electron traps and double exchange interactions: Mn3+—O2—Mn4+.
The Case of Pr0.7Ca0.3MnO3 
FIG. 6 is a drawing depicting the band gap as a function of x value and oxygen vacancies. According to experimental data, Pr0.7Ca0.3MnO3 has a maximum concentration of Mn3+ ions (8%) in CaMnO3 subunits and oxygen vacancies (4%), as summarized in Table 1. Moreover, the composition of Pr0.7Ca0.3MnO3 is located at the boundary between larger and smaller orthorhombic distortion, D, as x is varied in Pr1−xCaxMnO3. In PCMO materials, in the composition range 0<x<0.4, the materials are known to have lower resistance. Conversely, for x>0.4, PCMO materials have higher resistance. Similarly, Pr0.7Ca0.3MnO3 is also located at the boundary between higher and lower resistance materials. From the characteristics of Pr0.7Ca0.3MnO3 materials, it can be concluded that for x>0.4, the band gap of PCMO materials is so large that it is difficult to electrically alter the material resistance. Conversely, in the composition range 0<x<0.2, PCMO materials are leaky or conductive.
In the composition range 0.2<x<0.4, the resistance of the material becomes metastable, which allows electrical alteration of the resistance. Also, a pulsed electric field can cause electrons to jump into oxygen vacancies, or to transfer from Mn3+ to Mn4+. In this case, the resistance of PCMO increases. Conversely, if in a pulsed electrical field, electrons transfer back from oxygen vacancies to Mn3+, or from Mn4+back into Mn3+, then the resistance of PCMO decreases. Therefore, electrical alteration of the resistance in PCMO may be caused by electron trapping in oxygen vacancies and double exchange interactions: Mn3+—O2—Mn4+. In addition, as temperature is increased, thermally excited electrons may transfer into oxygen vacancies or make double exchange interactions Mn3+—O2—Mn4+. Thus, the resistance of PCMO materials decreases as a function of increasing temperature, as is observed.
FIG. 7 is a diagram depicting the distribution of PrMnO3 and CaMnO3 subunits, as a function of x, in Pr1−xCaxMnO3 materials. In PCMO for any value of x, there are ordered distributions of PrMnO3 and CaMnO3 subunits. PrMnO3 and CaMnO3 subunits are separately grown layer-by-layer depending on the ratio of PrMnO3 to CaMnO3. For x=1⁄2, PrMnO3 subunits alternate with CaMnO3 subunits. For Pr0.7Ca0.3MnO3 materials, which is close to x=1⁄3, typically two PrMnO3 subunit layers are separated by one CaMnO3 subunit layer. Likewise, for x=1⁄4, three PrMnO3 subunit layers are separated by one CaMnO3 subunit layer. Because CaMnO3 subunits have Mn3+ ions and oxygen vacancies, a double exchange interactions: Mn3+—O2—Mn4+may occur between of PrMnO3 and CaMnO3 subunits. Pr0.7Ca0.3MnO3 may be changed by an applied electric field from an insulator to a conductor, or vice versa. Therefore, these materials exhibit a non-volatile, electrically alterable resistance.
Oxygen Vacancies
FIGS. 8A and 8B are drawings showing the direction from Mn3+ ions in PrMnO3, to oxygen vacancies, oriented toward a top electrode. In FIG. 8A, a positive voltage is applied to the top electrode. In FIG. 8B, a negative voltage is applied to the top electrode. From above analysis, the ordering and orientation of PrMnO3 and CaMnO3 units and distribution of oxygen vacancies are very important for the electrically alterable resistive properties of PCMO materials. If the distribution of PrMnO3 and CaMnO3 subunits and oxygen vacancies are random, then material does not show a strong electrically alterable resistance. According to equation 3, CaMnO3 subunits may have Mn3+ ions and oxygen vacancies under certain conditions. Due to the distortion of PrMnO3 subunits, oxygen vacancies may be formed on the boundaries between CaMnO3 and PrMnO3 units.
FIGS. 9A and 9B are drawings depicting the direction of electron flow when opposite polarity pulses are applied to the top electrode. The free valence electrons of the Mn3+ ions transfer to oxygen vacancies if a positive pulsed voltage is applied to the top electrode (FIG. 9A). In this case, the material shows conductor properties. On the contrary, free valence electrons in oxygen vacancies transfer back to the Mn3+ ions if a negative pulsed voltage is applied to the top electrode at and the material shows insulating properties (FIG. 9B). If the directions from the Mn3+ ions to oxygen vacancies are oriented toward the bottom electrode, then the behavior relative to the potential of an applied pulse is reversed. In this way, electrically alterable resistive properties of PCMO materials may be obtained.
Double Exchange Interactions Mn3+—O2—Mn4+
FIGS. 10A and 10B are drawings showing the directionality of electron jumps between Mn3+ and Mn4+ ions. Alternatively, the formation of Mn3+ ions and oxygen vacancies in CaMnO3 units enhances the double exchange interactions Mn3+—O2—Mn4+between CaMnO3 and PrMnO3 unit layers. The free valence electrons of the Mn3+ ions in PrMnO3 subunit layers transfer to CaMnO3 subunit layers if a positive pulsed voltage is applied to the top electrode, and the material shows conductor properties. On the contrary, the free valence electrons in CaMnO3 subunit layers transfer back to PrMnO3 subunit layers if a negative pulsed voltage is applied to the top electrode, and the material shows insulating properties.
FIGS. 11A and 11B show electron flow when the PrMnO3 and CaMnO3 subunit layers are reversed with respect to the bottom electrode. Then, the material shows a behavior opposite of the behavior shown in FIGS. 10A and 10B.
The Relationship Between PCMO Composition and Electrically Alterable Resistance
Based on the above analysis, the composition of the Pr1−xCaxMnO3 thin films significant affect electrically alterable resistance properties. Experimental results show that PCMO materials with 0.1<x<0.6 exhibit electrically alterable resistance, and, in particular, PCMO materials with x=0.3, or close to this value, show the largest effect.
Crystallographic Orientation
The orientations of PCMO thin films show a significant affect upon electrically alterable resistance properties. Perfectly oriented and crystallized PCMO films, or epitaxial (single-crystal) PCMO with a smaller concentration of Mn3+ ions, have a higher resistance, and the largest change in resistance responsive to the application of an electric field. Due to higher activation energy (or barrier energy) for the transfer of electrons between Mn3+ and Mn4+, a higher operation voltage is required and the non-volatile (retention, endurance, etc.) properties are good. Of course, a reduction of the film thickness can reduce operation the voltage, which allows the resistance of the alterable resistor to be set at an optimum value. For perfectly oriented and crystallized PCMO films or epitaxial PCMO thin films, the main electrically alterable resistance properties of PCMO materials come from double exchange interactions Mn3+—O2—Mn4+. Oxygen vacancies enhance the double exchange interactions Mn3+—O2—Mn4+. This is the so-called bipolar case, for which resistance is raised and lowered reversibly by the application of short duration pulses of opposite polarity.
The orientation plays an important role in the bipolar switching properties. Table 2 shows the density of Mn atoms and the nearest distance between two Mn atoms, along with orientations. According to calculations, the PCMO thin films with (110) and (001) orientations have the best bipolar switching properties.







TABLE 2







The densities of Mn atoms and distance between


two Mn atoms of PCMO materials











Distance between two Mn



Densities of Mn atoms
atoms


Orientation
(number per 100 Å2)
(Å)





(100)
4.75
5.426


(010)
4.80
5.478


(001)
6.73
3.840


(110)
6.76
3.855


(011)
3.91
6.690


(101)
3.36
6.647









FIGS. 12A, 12B, 12C depict the (110), (011), and (101) orientations, respectively, of PCMO thin films. FIG. 12A shows the (110) orientation (marked ABCD) of a PCMO thin film. From the figure, the highest density of 6.76 per 100 Å2 area of Mn atoms and shorter distance (about 3.855 Å) between two Mn atoms lies along the (110) direction. Therefore, the strongest electrically alterable resistance can be obtained. Due to the lower density of Mn atoms and longer distance along (011) or (101), electrically alterable resistive properties will be weaker for films oriented in these directions, as shown in FIGS. 12B and 12C, respectively.
FIG. 13 shows an x-ray pattern of PCMO with partial (110) orientation. The sample shows good bipolar switching properties.
FIGS. 14A and 14B depict the (100) and (010) orientations of PCMO thin films, respectively. FIG. 14A shows the (100) orientation (marked ABCD) of PCMO thin films. Compared with (110) orientation, the density of 4.75 per 100 Å2 area of Mn atoms along the (100) direction is lower than in the (110) orientation, and the distance (about 5.426 Å) between two Mn atoms of (100) orientation is longer than that of (110) orientation. Therefore, the switching properties of (110) orientation are better than (100) orientation. In addition, the (010) orientation is similar to (100) orientation, as shown in FIG. 14B.
FIG. 15 shows the (001) orientation (marked ABCD) of PCMO thin films. Compared with (110) orientation, the density of 6.73 per 100 Å2 area of Mn atoms along with the (001) direction is similar to (110) orientation, and the distance about 3.84 Å between two Mn atoms is also similar to (110) orientation. Therefore, the switching properties of (110) orientation are similar to the (001) orientation.
FIG. 16 shows the x-ray pattern of PCMO thin films with (001) orientation.
FIG. 17 depicts the EDX pattern of the PCMO thin film of FIG. 16.
FIG. 18 depicts the switching properties of c-axis oriented PCMO thin films. The sharp (002) peak (FIG. 16) confirms the formation of C-oriented PCMO thin film. The energy dispersion x-ray analysis (EDX) measurement shows that the composition of the PCMO thin film is close to Pr0.7Ca0.3MnO3, as shown in FIG. 17. The PCMO thin film shows very good bipolar switching properties, as shown in FIG. 18, which is consistent with the above calculations.
The use of oriented polycrystalline PCMO films may result in a reduction in the operation voltage. But the resistance and ratio of higher resistive state to the lower resistive state is also decreased, and retention and endurance may be degraded.
By increasing Mn3+ ions, defects such as oxygen vacancy occur, and the barrier energy for transformation of electrons between Mn3+ and Mn4+decreases. Therefore, resistance and operation voltage may decrease, but retention properties may be degraded. If the ratio of Mn3+/Mn4+ ions is too high, the CMR materials are conductive.
The amount, distribution, and orientation of oxygen vacancies and defects have an effect upon switching properties. The distribution and orientation of groups of PrMnO3 and CaMnO3 have an affect upon the switching properties. There are optimum ratios of about 1-4 of Mn3+/Mn4+ and Pr/Ca for RRAM applications.
Crystallization and Switching Properties
When perfectly crystallized PCMO materials change into polycrystalline or amorphous PCMO materials, the oxygen vacancies and defects increase. The main reversible resistive switching mechanism of PCMO materials includes electron exchange or electron trapping between Mn3+—O2—Mn4+, and oxygen vacancies or defects, resulting in unipolar switching.
FIG. 19 shows the x-ray pattern of a PCMO thin film with nanosized polycrystalline materials. Based on calculations, the PCMO gain size is about 40 nm.
FIG. 20 depicts the unipolar switching properties of the PCMO thin film of FIG. 19. The write, high resistance state is achieved by applying 5V for 100 ns. The erase, lower resistance state results from applying 3V for 10 μs.
FIG. 22 is a flowchart illustrating the present invention method for forming a PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics. Although the method is depicted as a sequence of numbered steps for clarity, no order should be inferred from the numbering unless explicitly stated. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. The method starts at Step 200.
Step 202 forms a Pr3+1−xCa2+xMnO thin film composition, where 0.1<x<0.6. Step 204, in response to the selection of x, varies the ratio of Mn and O ions as follows:

    
    
        O2−(3±20%);
        Mn3+((1−x)±20%); and,
        Mn4+(x±20%).
    
    


If Step 202 forms a PCMO thin film with a Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96 composition, then Step 204 varies the ratio of ions as follows:

    
    
        O2−(2.96);
        Mn3+((1−x)+8%); and,
        Mn4+(x−8%).
    
    


In one aspect, a further step, Step 206 forms a 13.3% oxygen vacancy in the PCMO film.
FIG. 23 is a flowchart illustrating a second aspect of the present invention method for forming a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film with predetermined memory-resistance characteristics. The method starts at Step 300. Step 302 forms a PCMO thin film with a crystallographic orientation. Step 304 creates a density in the PCMO film, responsive to the orientation.
In one aspect, Step 302 forms a PCMO film in a (110) orientation. Then, Step 304 creates a density in the range of 5 to 6.76 Mn atoms per 100 Å2 in a plane perpendicular to the (110) orientation. In one aspect a further step, Step 306, creates a distance of 3.855 Å between the two closest Mn atoms in response to the (110) orientation.
If Step 302 forms a PCMO film in a (001) orientation, then Step 304 creates a density in the range of 5 to 6.73 Mn atoms per 100 Å2 in a plane perpendicular to the (001) orientation, and Step 306 creates a distance of 3.840 Å between the two closest Mn atoms in response to the (001) orientation.
FIG. 24 is a flowchart the present invention method for forming a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film memory-resistance device. The method starts at Step 400. Step 402 forms a bottom electrode from a material such as Pt, Ir, Al, or TiN. Step 404 forms a PCMO thin film with a crystallographic orientation overlying the bottom electrode. Step 406 creates a lattice mismatch in the PCMO film, responsive to the orientation, between the PCMO thin film and the bottom electrode. In some aspects, Step 403 forms a buffer layer interposed between the PCMO thin film and the bottom electrode formed from a material such as InO2 or ZnO.
If Step 402 forms a PCMO film in a (110) orientation, then Step 404 creates a lattice mismatch of less than 30% between the PCMO thin film and the bottom electrode. If Step 402 forms a PCMO film in a (001) orientation, Step 404 also creates a lattice mismatch of less than 30% between the PCMO thin film and the bottom electrode.
FIG. 25 is a flowchart illustrating a fourth aspect of the present invention method for forming a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film with predetermined memory-resistance characteristics. The method starts at Step 500. Step 502 forms a PCMO thin film with a crystallographic orientation. Step 504 creates a PCMO film with a selectable resistance state, responsive to the orientation.
If Step 502 forms a PCMO film in a (001) orientation, then Step 504 creates a PCMO film with a selectable resistance state, responsive to the orientation, by:

    
    
        writing a high resistance in the range of 10 to 1000 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds; or,
        resetting a low resistance in the range of 500 ohms to 10 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds.
    
    


If Step 502 forms a PCMO film in a (110) orientation, then Step 504 creates a PCMO film with a selectable resistance state, responsive to the orientation, by:

    
    
        writing a high resistance in the range of 10 to 1000 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds; or,
        resetting a low resistance in the range of 500 ohms to 10 kilo ohms, using ±(2 to 10) V pulse, with a duration in the range of 5 ns to 50 microseconds.
    
    


FIG. 26 is a flowchart illustrating a fifth aspect of the present invention method for forming a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film with predetermined memory-resistance characteristics. The method starts at Step 600. Step 602 forms a PCMO thin film with a crystal grain size. Step 604 creates a PCMO film with a selectable resistance state, responsive to the grain size.
If Step 602 forms a PCMO film with a crystal grain size in the range of 3 to 40 nm, then Step 604 creates a PCMO film with a selectable resistance state, responsive to the orientation, by:

    
    
        writing a high resistance of greater than 225 kilo ohms, using 5 V pulse of less than 100 ns; or,
        resetting a low resistance of less than 10 kilo ohms, using a 3 V pulse of less than 10 microseconds.
    
    


If Step 602 forms a PCMO film with a crystal grain size in the range of 40 nm to epitaxial, then Step 604 creates a PCMO film with a selectable resistance state, responsive to the orientation, by:

    
    
        writing a high resistance of greater than 300 kilo ohms, using −5 V pulse of less than 50 microseconds; or,
        resetting a low resistance of less than 10 kilo ohms, using a +5 V pulse of less than 50 microseconds.
    
    


FIG. 27 is a flowchart illustrating a sixth aspect of the present invention method for forming a Pr3+1−xCa2+xMn3+(1−x)±20%Mn4+x±20%O2−3±20% (PCMO) thin film with predetermined memory-resistance characteristics. The method starts at Step 700. Step 702 forms a PCMO thin film with a composition. Step 704 creates a super lattice structure with an ordered distribution in the PCMO film, responsive to the composition.
If Step 702 forms a PCMO thin film with a Pr3+0.50Ca2+0.50MnO0.3 composition, then Step 704 creates a distribution of:
Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
If Step 702 forms a PCMO thin film with a Pr3+0.67Ca2+0.33MnO0.3 composition, Step 704 creates a distribution of:
2Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
If Step 702 forms a PCMO thin film with a Pr3+0.75Ca2+0.25MnO0.3 composition, Step 704 creates a distribution of:
3Z(Mn3+)PrMnO3:Z(Mn4+)CaMnO3 subunits, where Z is a natural number.
PCMO thin films and associated formation processes have been presented. Some examples of resistance-memory characteristics, and related features, have been presented cross-referenced to PCMO film attributes to clarify the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.

## Claims

1. A method for forming a PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics, the method comprising:
forming a Pr3+1−xCa2+xMnO thin film composition, where 0.1<x<0.6;
in response to the selection of x, varying the ratio of Mn and O ions as follows:
O2−(3±20%);
Mn3+((1−x)±20%); and,
Mn4+(x±20%).

2. The method of claim 1 wherein forming a PCMO thin film with a composition includes forming a PCMO thin film with a Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96 composition;
wherein varying the ratio of Mn and O ions includes varying the ions as follows:
O2−(2.96);
Mn3+((1−x)+8%); and,
Mn4+(x−8%).

3. The method of claim 2 further comprising:
forming a 13.3% oxygen vacancy in the PCMO film.

4. A PrCaMnO (PCMO) thin film with predetermined memory-resistance characteristics, the PCMO thin film comprising:
a Pr3+1−xCa2+xMnO composition, where 0.1<x<0.6; and,
a ratio of Mn and O ions as follows:
O2−(3±20%);
Mn3+((1−x)±20%); and,
Mn4+(x±20%).

5. The PCMO thin film of claim 4 wherein the composition is Pr3+0.70Ca2+0.30Mn3+0.78Mn4+0.22O2−2.96; and,
wherein the ratio of Mn and O ions is as follows:
O2−(2.96);
Mn3+((1−x)+8%); and,
Mn4+(x−8%).

6. The PCMO thin film of claim 5 further comprising a 13.3% oxygen vacancy.