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Optically tuning TC in any superconductor

Article · January 2010

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 this study we use EEM to predict and
compare Tc enhancement in 8-PHASES of
OPTICALLY TUNING TC IN ANY TBCCO and Hg-TBCCO and Pb-Sr-
TBCCO-HTS-(TBCCO-2122,2212,2213,
SUPERC ONDUCTOR and 2223,1212,1223,1234,1245) against the
proven YBCO with EEM. Since High-
S.Curatolo** critical-temperature (HTc) superconductors
CZT Inc. Lawrence Kansas 66044 USA like TBBCO, have important applications in
many electronic and electrical devices due to
no-resistance, low energy loss, exclusion of
Abstract magnetic fields and special quantum
electronic characteristics like the Josephson
The Excitonic Enhancement Mechanism [1] effect, this study shows an enhanced Tc of
has been demonstrated theoretically and Near Room Temperature for all TBCCO 4
experimentally by CZT Inc. as the theory for phases and for Hg-TBCCO. The
superconductivity in hole carrier systems observations of data behavior near the Dirty
like YBCO and BISCCO[5][6], and novel Limit are of much importance to the
ones like boron doped silicon[ and [2][3][4], shortcomings of the SI phase. This result
because excitons are like hydrogen atoms points to the ability to bridge the gap of the
and possess excited energy levels, these obvious well known limitations of Tl-Cu-
Cooper pair exchange particles can be based-HTS. A Near-Room Temperature
excited by suitable incoherent infrared light TBBCO will enable the less-optimum thin
[5][6], resulting in large enhancement of the film processes to be available affording a
superconductivity-transition temperature more economical superconductor with
[5][6]. It has been shown experimentally higher Tc performance and less power
that EEM Tc enhancement for bulk and thin demand, having more phase stability, easier
film YBCO, with optimum YBCO bulk manufacturability and wider applications.
system, and by observing the diamagnetism
before and after IR light was applied, that
1. Introduction
the transition temperature increased ~80°K,
from exactly as predicted by the EEM
Superconducting systems that are hole carriers
theory [5][6]. These original measurements
and considered to be BCS like boron doped
were independently verified on an oxygen silicon [4], are in fact EEM-Excitonic
deficient YBCO thin film (dirty Enhancement Mechanism, as their charge
superconductor-bose-eintein condensate) by carriers are predominantly p-state holes, and
measuring the transition temperature using both have an empty s-state conduction band
AC voltage versus temperature measurement above the valence p-band. Their relatively low
before and after IR light was applied. The Tc values, according to EEM, were a result of
transition temperature was independently smaller band gap and excitonic binding energies.
verified to increase by ~17°K, from 69.5°K These latter systems have some common features
to 86.5°K [5]. Because, the increase in Tc with the Cuprates, such as their charge carriers
has been shown to be exactly as the value are mainly ‘p’ orbital valence band holes, and
that their conduction band is an empty ‘s’ orbital
calculated by the EEM theory [6], it makes
state. It is worthy to note that the main reasons
the EEM theory an invaluable tool for pointed to their differences are first, the
studying and predicting Tc enhancement in substantially higher Tc value for some cuprates,
any cuprate based HTS with incoherent IR and secondly, the presence of the‘d’ orbitals in
stimulation [5]. As a result of these cuprates, which is absent in the other systems. In
experimental confirmations in YBCO, in the cuprates, it has been found also that the
superconducting Tc value is correlated to the
**
Corresponding author: Susana Curatolo, President number of CuO2 layers in its crystal structure,
CZT Inc. [email protected] with a maximum reached at 3 layers. On top of

1
this feature, Tc varies according with hole Our earlier work provided detailed discussion of
carrier density in an inverse parabolic the EEM Theory [5] [6] [1], particularly the two
dimensional model [1] [5] [6] developed
form. The Excitonic Enhancement Mechanism
specifically for the cuprate systems. Since EEM
or EEM [1] for the cuprates, also possesses these
has been proven for YBCO system theoretically
features [9]. Bismuth and thallium
and experimentally [1] [5] [6], and the aim of the
superconducting cuprates with structures related
current paper is to use this theory’s validity for
to the Aurivillius family of oxides with Tc’s in
YBCO and apply it to the TBCCO system,
the 100K region also possess these features.
including Hg-TBCCOs and Pb-Sr-TBCCOs. The
Thallium cuprates of the Tl-Ba-Cu-O-
implications from the behavior to BCS will be
2122,2212,2213,2223 systems show Tc onset in
discussed. We will discuss our complete analysis
the 100-120K region, with resistivity
based on the YBCO model, and calculate the TCU
susceptibility behavior as high as 130K for Tl-
enhancement for the various TBCCO systems.
Ba-Cu-O-2223(optimum thin film) sample[10].
All in all, we consider 19 superconductors using
The basic EEM is based on a two band model,
their optimum and deficient published values [6]
with a partially filled valence ‘p’ band, and an
[11] [12] [13] [14] [15] [16].This model is
empty ‘s’ conduction band, separated by a
transportable across HTS-Cuprates like BiSCCO
positive band gap G. In fact this theory model is
[5] [6], and theTl-Ba-Cu-O-2122, 2212, 2213,
satisfied by the actual band structures of all the
2223, 1212, 1223, 1234, 1245 we are about to
above-mentioned novel superconductors. Apart
present since they are based on the same cuprate-
from Tc, the EEM model also predicts other
geometry. The EEM theory is based essentially
novel properties in both the normal and
on the dipolar interband interaction between an
superconducting phases, such as the sign
intrinsic partially filled valence ‘p‘ band from the
changes that were observed in the mixed-state
Oxygen ions and the empty conduction ‘s ‘ band
quantum Hall effect [10], and the thermal
electric power [11].It has already been of the Ba/Sr ions, which lay above the CuO2
determined experimentally and theoretically that layer. Since excitons have excited levels similar
this specific geometric model of EEM is able to to phonons, we therefore expect that if a large
produce the following properties known to be enough population of such excited excitons are
associated with cuprates like YBCO[1][6] and maintained, Tc can be enhanced [5][6]. So, the
now to other cuprates Tl-Ba-Cu-O-2122, 2212, renormalized band structure results as given in
2213, 2223,1212, 1223, 1234, 124 5. First, Tc reference [1] [5] [6]. The KEY Equations [1] [5]
correlation to carrier density and the number of [6] are used in this study to perform the
CuO2 layers [1][6], as mentioned earlier. It is, calculations and analysis on the TBCCO systems.
The excitons are stable if and only if, its binding
therefore, our intention in this paper to predict
energy exceeds the thermal fluctuation energy,
that the presence of excitons in Thallium based
which creates them in the first place. Should this
cuprate HTS behavior and that it is the same
condition be satisfied, global formation of
pattern as YBCO which was proven
localized excitons will occur in the structure,
experimentally[5][6]. The exciton contribution
quite similar to the phonon lattice. Because
to superconductivity has been verified
excitons are Bosons, when coupled to the mobile
experimentally through infrared light irradiation
holes can replace the phonons in the BCS theory,
[5] [6]. I present the analysis and calculation for
and lead to hole-hole Cooper pairing, thus
the TBCCO system using the EEM YBCO
producing superconductivity [5] [6].
model which predicts an enhancement to near
Consequently, to obtain Tc based on exchange of
room temperature for some of the TBCCO
excitons, we first obtain the exciton’s excitation
systems. I explain the positive consequences of
the enhancement in terms of the system’s known energy, [5] [6]], which is given by !3 minus the
phase instabilities in the deficient range, the exciton binding energy to the lattice !! . It is
dirty limit and in the dirty range before system important to note that the excitonic binding to the
collapse. lattice vanishes along the cell diagonals. The
space average value of which is of order eV, and
2.Theoretical analysis and calculation is quite stable in the superconducting phase.
of TBCC O using EEM Theory Hence the lateral thermal fluctuation that
destabilizes the bound exciton occurs in the
normal phase. Because the excitonic levels of the

2
system are inside the band gap, it implies such separate cases. These two cases Optimum and
exciton is localized or bounded to the crystal Deficient will govern the subsequent calculations
lattice. Hence, when the exciton is delocalized, it for TBCCO exactly, we just use the
will decompose into a free electron and a free corresponding Tc to the corresponding
hole. Such a picture for the normal phase gives superconductor. First, with the optimum YBCO
raise to the two carrier’s model [5] [6].]This sample [5][6], and the optimum TBCCO sample,
bound excitonic excitation energy !! now and n = no , then
replaces the Debye phonon energy in the Cooper
$ 26 # " 2 18 '
pair BCS energy gap ! BCS . Since the
&% 9 " # 13 )(
superconducting Tc is directly proportional to the
( )
Tc * no = optTc !
4
= optTc * ,
! BCS , it follows for the cuprate, Tc is
HTSOPT
BCS gap
#
proportional to the exciton excitation energy. It is and we get, regardless of system and phase:
precisely this feature that allows EEM to explain
the Tc dependence on the hole density[5][6]. The Tc* !"1
photo-excitation necessary to excite the excitons
HTSOPT ! = 1.870967742 . For
Tc !"
into the first excited level is of energy [5][6] of
8 YBCOOPT !" = 0.1 we obtained a maximum
!! 1 = E . Since, this photon energy is the enhancement of ~90% of Tc[5][6], see Fig.2,
9 o and Fig.1 for NOS Tc behavior only. The Second
same for exciting the system from either above or
case (see Fig.1): For the O2-deficient range
below Tc, as G * ! 0 and !! 1 is of order 1 eV, (BoxII), Dirty Limit(DL) and Dirty(BoxIII),
it follows the photon wavelength is much larger (dirty-HTS = maximal-defects-BCS like) YBCO-
def Tc = 70 K [5][6] and for the O2-deficient
!
than the crystal cell dimensions. Hence when we
pump the system with such IR photons [5][6], the TBCCOs see Fig.1. Now need to find the oxygen
populated electrons with the highest energy level
are excited. There is a difference where these deficient factor !" #
(n o
$n ) for EACH of
electrons are located depending on the system’s no
physical phase. Given that the proportionality of
these samples. First. !" is obtained from our
Tc on the exchange exciton excitation energy
equation using the values for optTc and defTc
!!1 and assuming J and N F* remain relatively from the sources obtained for each
constant, we can estimate the enhancement of Tc superconducting system
[6][10][11][12][13][14][15][16],and-by-
Tc* !"1
to Tc* from the ratio[5][6] of
Tc
!
!"
. It
comparing () ( )
Tc n to Tc no -that is, defTc to
follows that, how much Tc is enhanced to Tc* optTc, and solving for !" we get all the
depends critically on the sample’s original Tc corresponding values listed in Table.1.( See
value obtained from experimental sources for our
study, because Tc of the sample is dependent on Fig.1). Then substituting !" into Eo [1][5][6],
the ‘p’ hole density n [5][6], through the we obtain
excitonic excitation energy shown here [5][6] ) %
'' $ !2 ''
( )8
( ) 4
2 2
!! , with Eo as optimum excitonic ground state *2 ! "# + 1! "# ! &
$
' 9 8
( ) ( ) '
2 2

()
Tc * n '+ 2 ! "# + 1! "#
9 '( .
16Rm * 2 =
binding energy [5] given as Eo ! no . ( )
Tc no 4
$
"2
Thus, using this equation [1][5][6] we get !"
In our previous work in YBCO [1][5][6], the
for all 19 superconductors. Fig.1a&1b shows
! ( ) = 2.07 eV " 2Eo . .So, in order to
o
that NOS Tc behavior for under-doped and over-
prepare at this point, to perform TBCCO Tc doped sample conditions, and they are mirror-
enhancement calculations and compare against images. BoxI-II&III are the same for - !" .
our previous and proven study of infrared light Figure.2.compares NOS-&-OS Tc Enhancement
enhancement on YBCO [5][6] on the critical ratios vs !" , and we clearly observe the
temperature, namely Tc*, we consider two

3
linearization under OS conditions, following
the same pattern observed for the YBCO system
and BISCCO[1][5][6], and that for ovedoping it
is a mirro-image. In fact, the non-coherent- Fig.2a Mirror- NOS & OS Tc Enhanced Ratio vs !"
infrared light(not a laser)[5][6] is able to
stimulate Tc enhancement even when sample is Fig.2b NOS & OS Tc Enhanced Ratio vs !"
under-doped or over-doped in BoxII and DL,
enhancing Tc ! 20% within BoxII, < 20%
within DL(dirty limit: underdoped or NOS & OS Tc Enhancement Ratios
2.0
overdoped), and losing enhancement in BoxIII.
Because we have normalized by dividing over 1.8

Tc Enhancement Ratio
optTc, Fig2a,b is universal for all cuprates! 1.6 I
Then,
1.4

1.2 II
defTc*/optTc
Tc!DL " Tc!DEF ( #$ =0.38to0.53) " Tc!MID( #$ =0.1to0.38) " TcOPT
!
( #$ =0to0.1) 1.0 DL
Tc!DL( #$ = %0.53to%0.57) " Tc!MID( #$ = %0.1to%0.38) " TcOPT
!
( #$ =0to%0.1) 0.8
defTc/optTc III
0.6
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
delta-etaI-II-III

Fig.1.a Mirror-Image NOS Tc behavior vs !"

Fig.1.b NOS Tc Behavior vs !"

Tc against Sample Oxygen Deficiency

(non-optically stimulated)
5
Box I !" # 0.1 ! Tc* $ 90%
137K
138K Box II !" # 0.5 ! Tc* $ 20%
80K Box III !" $ 0.57 ! Tc*< Tc(n)
Tc in relative units

4 79.5K
118K
(I) OPTIMUM

112K K
109
3
70K
95K
(II) DEFICIENT

70K
(III) DIRTY

0
0.0 0.2 0.4 0.6 0.8 1.0

oxygen deficiency ratio !"

Fig.3 Phase diagram showing the under-doped and

over-doped regions of various Cuprate systems[1]

Sum mary Discussion and

Co nclusions

NOS Behavior In Fig.1 a & b, we start first

with the Tc vs !" I-II-III. This plot is intended
to show the behavior of Tc for the standard

4
normalized for optimum at !" = 0.0-0.1 (Box photon of energy at least equal to E . For the
I), under doped and over doped deficient range : YBCO system, E is approximately 1 eV. Since
the natural relaxation of the excited state is
!" ± =0.38-0.5-0.53 (Box II), dirty limit range independent of the wavelength intensity, and Tc*
: !" ± = 0.53-0.57 (DL) , dirty range : !" ± = is wavelength intensity dependent, then the key
0.57-0.7. This curve is also valid for over-doping is to maintain equilibrium. Since the optical
(- !" ). So the shape is the same, but a mirror dependent excitation rate and the density of
excited excitons are related to one another, and
image from 0.0. The Tc values are for highest
with enough IR photons uniformly absorbed over
and lowest for each range, for the Tc and defTc
the entire surface of the HTS material film Tc* is
values from the literature sources consulted. We
realized. since the superconducting Tc is directly
can observe in Fig.(1) very clearly the non-
enhanced [high,low] limits of Tc for each range. proportional to the BCS gap ! BCS , it follows
For Box-I : 138°K,80°K-137°K,79.5°K; Box-II : for the cuprate sytem, that Tc is proportional to
112°K,70°K-118°K,95°K; 118°K,95°K < DL < the exciton excitation energy [5][6]. So, the
109°K.70°K; Box III > 109°K,70°K . The defTc*/optTc ratios against the oxygen
defTc/optTc vs !" in Fig.2a,b demonstrate the deficiency ratio !" show basically a linear
Tc behavior deficient/optimum ratio versus relationship. For BoxI the ratio is between 1.7-
sample oxygen deficiency ratio. For Box I the 1.85-0.98, for BoxII the ratio is between 1.25-
ratio is between 0.98-1.0, for BoxII the ratio is 0.98, for DL the ratio is between 0.92-0.82, and
between 0.775-0.875, for DL the ratio is between for BoxIII the ratio is 0.82-0.73. The difference
0.845-0.825, and for BoxIII the ratio is 0.815- in ratios between NOS defTc/optTc and OS
0.775. Notice the splitting at !" = 0.5-0.53 defTc*/optc is on the order of a factor of 2 BoxI,
where the deficient range ends and the Dirty whereas the difference is about 1.5 for BoxII,
Limit begins. This is critical because it is where and it drops to 1.25 for DL and the difference in
we observe SI (superconductor-insulator phase) ratios for Box-III is 0.9 where the Tc* is below
behavior causing Tc to drop for both underdoped Tc. This indicates that the enhancement responds
and over-doped. It is an area where the material within the predicted enhanced limits and the
behaves like a BCS-Bose-Einstein Condensate, proportionality of the enhancement to the exciton
and superconductivity is lost, particularly true energy. The difference between NOS and OS
for metal-insulator type metal oxides. Oxides are ratios for the different !" ranges can be clearly
perceived in the industry as having inherent seen in that the OS linearizes the response and
unstable nature[12]. There are manufacturing we have the corresponding enhancements of
issues too, intrinsic local stoichometric -defects 20% for def under-doped and over-doped, 10%
arise in HTS from the insertion of cations in the for DL under-doped and over-doped as opposed
wrong layer and defects of the oxygen sublattice, to 90% for the optimum. These represent a
forcing manufacturing to adjust oxygen content significant broadening of the phase diagram of
in compound-specific off stoichiometric ratio in the experimental data sources seen in Fig.3 by as
order to optimize the superconducting
much as no (1 ± 0.89) , and thereby exceeding
properties[10]. This we shall see, is very much
mitigated using incoherent-Near-IR to achieve the industrial averages substantially. We seek
superconductivity in the SI range as opposed to industrial deployment of these films given the
far-IR-stimulated Cu-O plane[17].Over-doping obvious advantages in the SI as compared to
and Under-doping mirror each other based on literature.
this method. The manufacturing advantage is
obvious from a production and quality control References
point of view. OS Behavior No parameter
[1] K.W.Wong,W.Y.Ching,Physica C, 416
adjustments are necessary, for the cuprate
(2004) 47
geometry of the band structure provides the
[2]I.N.Makarenko,D.V.Niforov,A.B.Kykov,O.K.
means for calculating the deficiency ratio and the
Mel’nikov,S.M.Stishov,’
Tc*, given a Tc for that superconductor. The
Anisotropy of the electrical resistance of single
incoherent IR λ is calculated based on equation
crystals of Htc YBCO’, Pis’ma
(29) of [5][6] . As excitons can be excited, they Zh. Eksp. Theor. Fiz. No.1, 52-56, 1988, USSR.
can also be destroyed. To destroy the excitons [3] J.G.Bednorz and K. A.M ulller,’Perovskite –
we irradiate them with incoherent-near-IR type oxides-the new approach to

5
 HTcSC’,Rev. Mod. Phys.Vol.60,No.3,July 1988 CSC&ESASEuropean-Superconductivity-News-
[4]Cava Lab: Intermetallic Superconductor Forum-(ESNF), No.12, April 2010,p.7-9
research
[5] Susana Curatolo, Kai Wai Wong,-USPatent
No.20080293577,IPC8
Class:AH02H700FI,USPC Class: 505850;Title:
Method for Operating a Superconductor at a
Temperature Higher than the Superconductive
Temperature Tc.
[6] S.Curatolo,K.W.Wong,Progress in
Superconductivity-EEM:The Exciton
Enhancement Mechanism Theory and
Experimental Evidence of Optically
Enhanced Tc in High Tc
Superconductors’.ISBN 978-1-60021-694-7,
2008. Nova Science Publishers Inc. Oliver
Chang- Editor
[10] Hott, Roland; Narlikar,A.V.-High
Superconductivity 1-Materials;Table-1, page 4,
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[11]Rao, C.N. High Temperature Ceramic Oxide
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July 1988, pp.19-35.Table 10, p.29.
[12] S. A. Sunshine and T.A. Vanderah.
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China Lake, CA 93555 Office of Naval
Research. Grant Contract N00014-91WX-
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REPORT NO.2 Published in ‘Chemestry of
Oxide Superconductors’ by T.A. Vanderah.
Noyes Publications, 1991. Table 1, p.5
[13] DuPont Superconductivity : Development
of High temperature Superconducting Josephson
Junction Device Technology-Final Report
January 1996-January 1998 Program Manager
Kirsten E Myers; In situ deposition
Thallium-containing oxides. K.E.Myers Du Pont
CR&D Experimental Station-E304/C110
Wilmington DE, USA;page168/SPIE
Vol.2697:Sections 4.3 and 4.4.
[14]-B.R.Xu, Y.Xin, G.F.Sun, K.W.Wong, XII-
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Phys.Lett. A 192 (1994)p122-124
[15] F. Gouternoire et al, ‘Substitution of Hg for
Tl in Hg-Tl-BCCO-2223’,Solid State
Communications 90(1,)April-1994, p.47-51
[16] Hur, Yong Hi Park, K J Park,Jong
C.(Daejeon) US Patent No. 5492885, 1995
[17] Vaglio, Ruggero ‘The New Italian CNR
Institute SPIN’, CNR-SPIN/IEEE-

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